CN102229553A - Multistage rearrangement system and method for preparation of caprolactam from cyclohexanone oxime - Google Patents
Multistage rearrangement system and method for preparation of caprolactam from cyclohexanone oxime Download PDFInfo
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 294
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008707 rearrangement Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims description 52
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims description 41
- 239000012442 inert solvent Substances 0.000 claims description 21
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 17
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 6
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 2
- 238000006462 rearrangement reaction Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 84
- 150000002923 oximes Chemical class 0.000 description 21
- 230000009466 transformation Effects 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 238000003556 assay Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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Abstract
The invention discloses a multistage rearrangement system and a method for preparation of caprolactam from cyclohexanone oxime, and belongs to the technical field of organic compound synthesis. The method employs a plurality of micro mixers in series to realize Beckman rearrangement process through multistage. In a first micro mixer, 6-30 wt% of oleum is used as a disperse phase, and cyclohexanone oxime is dissolved in an inertia solvent to be used as a continuous phase; the disperse phase and the continuous phase are mixed to initiate a rearrangement reaction, and continue to react with replenished cyclohexanone oxime in micro mixers from No.2 to No.4; and two adjacent micro mixers are in series and connected by pipelines. Reaction materials flow out from a last micro mixer, and are slaked for 40-120s thorough pipelines, then are sent for hydrolysis reaction to separate the inertia solvent and the caprolactam. Utilizing the method, process security can be further enhanced; cycle operation can be avoided; and output of a by-product ammonium sulfate can be reduced substantially.
Description
Technical field
The invention belongs to the organic compound synthesis technical field, be specifically related to the system and method for a kind of multistage rearrangement by preparing caprolactam with cyclohexanone-oxime.
Background technology
ε-Ji Neixianan is a kind of important Organic Chemicals, is mainly used in to produce nylon 6 fiber (polyamide fibre 6) and nylon 6 engineering plastic.Wherein: nylon-6 fiber is widely used in industries such as wool spinning, knitting, woven, carpet, and nylon 6 engineering plastic is widely used in industries such as electronics, automobile, packaging film.
It is the at present industrial technology of generally using that cyclohexanone-oxime is converted into hexanolactam through the liquid phase Beckmann rearrangement, and the catalyzer of employing is generally the vitriol oil or oleum.Characteristics of Beckmann rearrangement are that thermal discharge is big, and temperature is wayward.The popular response device adopts outer circulation to come heat-obtaining, and its recycle ratio can be up to 245, and this causes equipment capacity low, running cost height, the security of reactor and reaction process and poor reliability.Another characteristics of Beckmann rearrangement are that sour oxime exists threshold value than (mol ratio of the vitriol oil or oleum and cyclohexanone-oxime), and the subcritical value can easily cause Beckmann rearrangement not exclusively to reach the generation side reaction.In the popular response device, mix the bad sour oxime that causes than imbalance for avoiding local, need to adopt sour oxime ratio, thereby can produce more low-value by-product ammonium sulfate apparently higher than threshold value.1.2 to 1.7 moles of low value byproduct of ammonium sulfate of typical rearrangement 1 mole of hexanolactam by-product of the every production of technology, and how to reduce ammonium sulfate by-product amount, be one of target of process modification always.
Along with science and technology development, microminiaturization becomes chemical process and important trend of equipment development.With respect to the popular response device, microreactor has the heat and mass transfer coefficient height, good mixing property, easy control of temperature and safe advantage.These advantages are combined with the characteristics of Beckmann rearrangement, adopt the one-pass operating method of reaction mass, be expected more strictly to control local temperature, proportioning and the reaction process of reaction system, be to improve the controllability and the security of reaction, further reduce sour oxime and recently reduce the ammonium sulfate by-product condition is provided.
Summary of the invention
The object of the present invention is to provide the system of a kind of multistage rearrangement by preparing caprolactam with cyclohexanone-oxime.
The present invention also aims to provide the method for a kind of multistage rearrangement by preparing caprolactam with cyclohexanone-oxime.
A kind of multistage is reset the system by preparing caprolactam with cyclohexanone-oxime, and this system adds flow container, oleum by cyclohexanone-oxime and adds flow container, first micro mixer, second micro mixer, the 3rd micro mixer, the 4th micro mixer and constitute; Ketoxime adds flow container and links to each other with first micro mixer, second micro mixer, the 3rd micro mixer, the 4th micro mixer respectively by pipeline; Oleum adds flow container and first micro mixer two connects; First micro mixer links to each other with second micro mixer, the 3rd micro mixer, the series connection of the 4th micro mixer successively.
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the inert solvent, is made into the solution that the cyclohexanone-oxime massfraction is 1-18%, join cyclohexanone-oxime and add flow container;
B, with oleum as disperse phase, cyclohexanone-oxime solution is as external phase, adds flow container and cyclohexanone-oxime by oleum respectively and adds flow container and inject first micro mixer, short mix also causes Beckmann rearrangement;
C, will feed second micro mixer, the 3rd micro mixer, the 4th micro mixer successively, continue reaction with mixing with the cyclohexanone-oxime solution of adding in second micro mixer, the 3rd micro mixer, the 4th micro mixer through the mixture behind the Beckmann rearrangement;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of last micro mixer.
Described inert solvent is normal hexane, normal heptane, octane, hexanaphthene or their mixture.
The total mol ratio that adds oleum and cyclohexanone-oxime among step b and the c is 0.6-2.
The feeding temperature of oleum is 70-110 ℃ among step b and the c, and the feeding temperature of cyclohexanone-oxime solution is 70-110 ℃.
The mass ratio of the feeding quantity of cyclohexanone-oxime solution is (0.4-0.8) in first micro mixer, second micro mixer, the 3rd micro mixer and the 4th micro mixer: (0.2-0.5): (0-0.2): (0-0.2).
Beneficial effect of the present invention: the stagnant storage of material is little in the micro mixer, resets technology by multistage, makes full use of the nicotinic acid catalytic, controls local temperature better, thereby improves the controllability and the security of Beckmann rearrangement; Whole multistage system for rearranging is avoided outer circulation, can strictly control the residence time, improves reaction preference; The multistage micro mixer is reset technology, can make the sour oxime that carries out Beckmann rearrangement than further reducing, and minimumly can reach 0.6, far below minimum sour oxime in the present technology than 1.2, thereby significantly reduce low value producing ammonium sulfate byproduct output.
Description of drawings
Fig. 1 is the system schematic of multistage rearrangement by preparing caprolactam with cyclohexanone-oxime;
Among the figure, the 1-cyclohexanone-oxime adds flow container, the 2-oleum adds flow container, 3-first micro mixer, 4-second micro mixer, 5-the 3rd micro mixer, 6-the 4th micro mixer.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is further specified, but not thereby limiting the invention.
Following examples all adopt multistage as shown in Figure 1 to reset system by preparing caprolactam with cyclohexanone-oxime, and this system adds flow container, oleum by cyclohexanone-oxime and adds flow container, first micro mixer, second micro mixer, the 3rd micro mixer, the 4th micro mixer and constitute; Ketoxime adds flow container and links to each other with first micro mixer, second micro mixer, the 3rd micro mixer, the 4th micro mixer respectively by pipeline; Oleum adds flow container and first micro mixer two connects; First micro mixer links to each other with second micro mixer, the 3rd micro mixer, the series connection of the 4th micro mixer successively.
The transformation efficiency and the selectivity of reaction are calculated according to following formula:
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, be that the oleum of 20wt.% is as disperse phase with SO3 content, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.1mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.9; Assay products, the transformation efficiency of reaction reaches 100%, and selectivity reaches 99.4%.
Embodiment 2
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 1% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 2.4mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 2.0; Assay products, the transformation efficiency of reaction reaches 100%, and selectivity reaches 99.9%.
Embodiment 3
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 18% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 2.0mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 70 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 70 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio of step b and c reaction is 0.9; Assay products, the transformation efficiency of reaction reaches 98.3%, and selectivity reaches 98.0%.
Embodiment 4
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 0.85mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.7; Assay products, the transformation efficiency of reaction reaches 98.2%, and selectivity reaches 99.0%.
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 0.9mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 25mL/min, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.66; Assay products, the transformation efficiency of reaction reaches 99.5%, and selectivity reaches 99.3%.
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 6wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.5mL/min, the external phase flow that injects first micro mixer is 25mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 80 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 80 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 1.07; Assay products, the transformation efficiency of reaction reaches 84.0%, and selectivity reaches 99.9%.
Embodiment 7
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 0.75mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 110 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 110 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.62; Assay products, the transformation efficiency of reaction reaches 100%, and selectivity reaches 98.9%.
Embodiment 8
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 30wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.1mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 70 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 70 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 1.0; Assay products, the transformation efficiency of reaction reaches 86.6%, and selectivity reaches 96.2%.
Embodiment 9
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.5mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 70 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 20mL/min, and temperature of reaction system is 70 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 1.23; Assay products, the transformation efficiency of reaction reaches 100%, and selectivity reaches 93.2%.
Embodiment 10
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 0.7mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer through the mixture behind the Beckmann rearrangement, and mix with the cyclohexanone-oxime solution of adding in second micro mixer and continue reaction, adding the external phase flow is 15mL/min, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of second micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.66; Assay products, the transformation efficiency of reaction reaches 76.1%, and selectivity reaches 99.2%.
Embodiment 11
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 0.7mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer, the 3rd micro mixer successively through the mixture behind the Beckmann rearrangement, mix the continuation reaction with the cyclohexanone-oxime solution of adding in second micro mixer, the 3rd micro mixer, it is 10mL/min that second micro mixer is added the external phase flow, it is 5mL/min that the 3rd micro mixer is added the external phase flow, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of the 3rd micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.77; Assay products, the transformation efficiency of reaction reaches 91.9%, and selectivity reaches 95.3%.
Embodiment 12
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.1mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer, the 3rd micro mixer successively through the mixture behind the Beckmann rearrangement, mix the continuation reaction with the cyclohexanone-oxime solution of adding in second micro mixer, the 3rd micro mixer, it is 10mL/min that second micro mixer is added the external phase flow, it is 10mL/min that the 3rd micro mixer is added the external phase flow, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of the 3rd micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.72; Assay products, the transformation efficiency of reaction reaches 96.3%, and selectivity reaches 98.7%.
Embodiment 13
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 0.9mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer, the 3rd micro mixer, the 4th micro mixer successively through the mixture behind the Beckmann rearrangement, mix the continuation reaction with the cyclohexanone-oxime solution of adding in second micro mixer, the 3rd micro mixer, the 4th micro mixer, it is 10mL/min that second micro mixer is added the external phase flow, it is 5mL/min that the 3rd micro mixer is added the external phase flow, it is 5mL/min that the 4th micro mixer is added the external phase flow, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of the 4th micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.74; Assay products, the transformation efficiency of reaction reaches 95.2%, and selectivity reaches 98.5%.
Embodiment 14
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.1mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer, the 3rd micro mixer, the 4th micro mixer successively through the mixture behind the Beckmann rearrangement, mix the continuation reaction with the cyclohexanone-oxime solution of adding in second micro mixer, the 3rd micro mixer, the 4th micro mixer, it is 20mL/min that second micro mixer is added the external phase flow, it is 10mL/min that the 3rd micro mixer is added the external phase flow, it is 10mL/min that the 4th micro mixer is added the external phase flow, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of the 4th micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.6; Assay products, the transformation efficiency of reaction reaches 94.2%, and selectivity reaches 98.8%.
Embodiment 15
A kind of multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the octane solution, is made into the cyclohexanone-oxime massfraction and is 10% solution, join cyclohexanone-oxime and add flow container;
B, with SO
3Content is that the oleum of 20wt.% is as disperse phase, cyclohexanone-oxime solution is as external phase, adding flow container and cyclohexanone-oxime by oleum respectively adds flow container and injects first micro mixer, the disperse phase flow is 1.1mL/min, the external phase flow that injects first micro mixer is 20mL/min, short mix also causes Beckmann rearrangement, and temperature of reaction system is 90 ℃;
C, will feed second micro mixer, the 3rd micro mixer successively through the mixture behind the Beckmann rearrangement, mix the continuation reaction with the cyclohexanone-oxime solution of adding in second micro mixer, the 3rd micro mixer, it is 10mL/min that second micro mixer is added the external phase flow, it is 10mL/min that the 3rd micro mixer is added the external phase flow, and temperature of reaction system is 90 ℃;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of the 3rd micro mixer.
The total acid oxime ratio that reacts among step b and the c is 0.72; Assay products, the transformation efficiency of reaction reaches 96.2%, and selectivity reaches 99.5%.
Claims (6)
1. a multistage is reset the system by preparing caprolactam with cyclohexanone-oxime, it is characterized in that this system adds flow container (1), oleum by cyclohexanone-oxime and adds flow container (2), first micro mixer (3), second micro mixer (4), the 3rd micro mixer (5), the 4th micro mixer (6) and constitute; Ketoxime adds flow container (1) and links to each other with first micro mixer (3), second micro mixer (4), the 3rd micro mixer (5), the 4th micro mixer (6) respectively by pipeline; Oleum adds flow container (2) and connects with first micro mixer (3) two; First micro mixer (3) links to each other with second micro mixer (4), the 3rd micro mixer (5), the 4th micro mixer (6) series connection successively.
2. a multistage is reset the method by preparing caprolactam with cyclohexanone-oxime, it is characterized in that, carries out according to following steps:
A, cyclohexanone-oxime is dissolved in the inert solvent, is made into the solution that the cyclohexanone-oxime massfraction is 1-18%, join cyclohexanone-oxime and add flow container (1);
B, with oleum as disperse phase, cyclohexanone-oxime solution is as external phase, adds flow container (2) and cyclohexanone-oxime by oleum respectively and adds flow container (1) and inject first micro mixer (3), short mix also causes Beckmann rearrangement;
C, will feed second micro mixer (4), the 3rd micro mixer (5), the 4th micro mixer (6) successively, continue reaction with mixing with the cyclohexanone-oxime solution of adding in second micro mixer (4), the 3rd micro mixer (5), the 4th micro mixer (6) through the mixture behind the Beckmann rearrangement;
D, behind pipeline slaking 40-120s, send to hydrolysis reaction, separate inert solvent and hexanolactam from the effusive reaction mass of last micro mixer.
3. according to the method for the described a kind of multistage rearrangement of claim 2, it is characterized in that described inert solvent is normal hexane, normal heptane, octane, hexanaphthene or their mixture by preparing caprolactam with cyclohexanone-oxime.
4. according to the method for the described a kind of multistage rearrangement of claim 2, it is characterized in that the total mol ratio that adds oleum and cyclohexanone-oxime among step b and the c is 0.6-2 by preparing caprolactam with cyclohexanone-oxime.
5. according to the method for the described a kind of multistage rearrangement of claim 2 by preparing caprolactam with cyclohexanone-oxime, it is characterized in that the feeding temperature of oleum is 70-110 ℃ among step b and the c, the feeding temperature of cyclohexanone-oxime solution is 70-110 ℃.
6. according to the method for the described a kind of multistage rearrangement of claim 2 by preparing caprolactam with cyclohexanone-oxime, it is characterized in that the mass ratio of the feeding quantity of cyclohexanone-oxime solution is (0.4-0.8) in first micro mixer, second micro mixer, the 3rd micro mixer and the 4th micro mixer: (0.2-0.5): (0-0.2): (0-0.2).
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| CN105017068A (en) * | 2015-07-06 | 2015-11-04 | 清华大学 | System and method for synthesizing cyclohexanone-oxime by micro-reactor |
| CN110511185A (en) * | 2019-09-17 | 2019-11-29 | 沧州旭阳化工有限公司 | Caprolactam rearrangement device and method |
| CN113121397A (en) * | 2021-04-20 | 2021-07-16 | 中国石油化工股份有限公司 | Method for preparing caprolactam from cyclohexanone oxime |
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| US5264571A (en) * | 1991-09-30 | 1993-11-23 | Basf Aktiengesellschaft | Preparation of caprolactam by Beckmann rearrangement of cyclohexanone oxime |
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| CN101434569A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Method and equipment for preparing caprolactam from cyclohexanone oxime |
| CN101851203A (en) * | 2010-03-03 | 2010-10-06 | 湘潭大学 | Method for continuously preparing hexanolactam by using cyclohexanone-oxime Beckmann rearrangement reaction |
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| US5264571A (en) * | 1991-09-30 | 1993-11-23 | Basf Aktiengesellschaft | Preparation of caprolactam by Beckmann rearrangement of cyclohexanone oxime |
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