CN102584776A - Method for preparing epsilon-caprolactone - Google Patents
Method for preparing epsilon-caprolactone Download PDFInfo
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- CN102584776A CN102584776A CN2011100055405A CN201110005540A CN102584776A CN 102584776 A CN102584776 A CN 102584776A CN 2011100055405 A CN2011100055405 A CN 2011100055405A CN 201110005540 A CN201110005540 A CN 201110005540A CN 102584776 A CN102584776 A CN 102584776A
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Abstract
The invention discloses a method for preparing epsilon-caprolactone, under the condition that solid acid catalyst exists, peroxide carboxylic acid solution is obtained by using hydrogen peroxide to oxidate organic carboxylic acid in a stirring reactor which has a fractionating column, the obtained peroxide carboxylic acid solution is reacted with cyclohexanone to obtain epsilon-caprolactone solution, then the high-purity epsilon-caprolactone is obtained after distillation and purification.
Description
Technical field
The present invention relates to-kind of the method for producing 6-caprolactone; This method is in the presence of solid acid catalyst; The aqueous peroxycarboxylic acid solution that organic carboxyl acid in the hydrogen peroxide oxidation organic solvent is obtained adds to react in the reaction system that pimelinketone is housed and obtains 6-caprolactone solution; In rectifying tower, separate then, realized the production of high-purity 6-caprolactone.
Background technology
In existing technology, 6-caprolactone prepares with peroxycarboxylic acid oxidation pimelinketone, and used peroxycarboxylic acid has Peracetic Acid and Perpropionic Acid etc., in common preparation method, generated various by products such as hexanodioic acid and 5-hexenoic acid, be difficult to from reaction product, separate obtaining high-purity 6-caprolactone.
In Japanese Patent 150681/1982, Japanese Patent 124781/1983 and Chinese patent ZL91109988.3, mentioned a kind of method; Wherein prepare stable 6-caprolactone with the peroxycarboxylic acid oxidation pimelinketone that contains 2～4 carbon atoms; Corresponding carboxylic acid and hydrogen peroxide react the form that obtains " the thick solution of peroxycarboxylic acid " with them in the presence of boric acid catalyst uses, and under azeotropic conditions, removes continuously and anhydrate.In this ordinary method; Because used the weak acid as boric acid; When comparing with the situation of using strongly acidic catalyst; The by product that generates can lack in the process of preparation 6-caprolactone, and still, the oligomer etc. that has still generated hydroxycaproic acid, 5-hexenoic acid, propionyloxy NSC 8882, hydroxy ethyl caproate and caprolactone in large quantities is difficult to isolating impurity.In the reaction of peroxycarboxylic acid and pimelinketone, react completely for making pimelinketone as far as possible, the mol ratio of peroxycarboxylic acid and pimelinketone causes containing in the distillation system the intact peroxycarboxylic acid of unreacted thus greater than 1, and the possibility that causes safety-problems increases greatly.
Summary of the invention
The contriver is through discovering; Though adopted this catalyzer of boric acid in the technology of existing preparation 6-caprolactone; But in reaction and purification process, this catalyzer but is present in the reaction system from start to finish, the particularly follow-up high temperature purification stage; Boric acid can promote the 6-caprolactone polymerization, thereby influences the purification of product.And ZL91109988.3 is in lab scale (being laboratory stage), reach the suitability for industrialized production stage also to exist many processing condition and problems such as need confirm.
The object of the invention aims to provide and a kind ofly prepares the method for 6-caprolactone with aqueous peroxycarboxylic acid solution's oxidation pimelinketone, and the influence that can effectively avoid catalyzer that 6-caprolactone is purified promotes in the commercial process of the present invention requirement to security simultaneously.
The present invention relates to a kind ofly prepare the method for 6-caprolactone, comprising with aqueous peroxycarboxylic acid solution's oxidation pimelinketone:
A. in the presence of solid acid catalyst; In the stirred autoclave of band rectifying tower, contain the mixing solutions of organic carboxyl acid and organic solvent with hydrogen peroxide oxidation; Mode through azeotropic distillation distills the water that the water of bringing in the superoxol and reaction process produce from cat head simultaneously, obtains containing the aqueous peroxycarboxylic acid solution of organic solvent from the tower still;
B. will add to the pimelinketone from the aqueous peroxycarboxylic acid solution that step a obtains and react, and make pimelinketone excessive, obtain 6-caprolactone solution;
C. will carry out rectifying through 4 rectifying tower from the 6-caprolactone solution that step b obtains, 6-caprolactone solution gets into tower A, distillates organic solvent and part organic carboxyl acid from cat head; Tower bottoms gets into tower B, distillates organic carboxyl acid and pimelinketone from cat head, and distillate gets into tower C again; Distillate organic carboxyl acid from cat head, the tower still obtains pimelinketone, and tower B still liquid gets into tower D; Distillate highly purified 6-caprolactone from cat head, the liquid that contains high-boiling-point impurity is discharged from the tower still;
Wherein used solid acid catalyst is acidic cation-exchange resin, perfluorinated sulfonic resin, molecular sieve, immobilized sulfuric acid, immobilized phosphoric acid or immobilized boric acid among the step a.
The mass ratio of solid acid catalyst and hydrogen peroxide is 0.01～1 among the step a, preferred 0.1～0.5.
Organic carboxyl acid is acetate and/or propionic acid among the step a.
Organic solvent is one or more in ETHYLE ACETATE, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, tert.-butyl acetate, ethyl propionate, propyl propionate, isopropyl propionate, ethyl n-butyrate, the ethyl isobutyrate, ethyl acetate and ethyl propionate among the step a.
The mol ratio of organic solvent and organic carboxyl acid is 0.1～10 among the step a, preferred 0.25～4.
The mol ratio of hydrogen peroxide and organic carboxyl acid is 0.1～1 among the step a, preferred 0.2～0.6.
Water among the step a from cat head distilled azeotrope is discharged system, and organic solvent is back in the tower.
Solid acid among the step a is stayed in the reaction kettle, does not contain solid acid catalyst among the aqueous peroxycarboxylic acid solution who from still, draws.
The temperature of reaction of peroxycarboxylic acid preparation is 10～90 ℃ among the step a, preferred 30～70 ℃.
The reaction times of peroxycarboxylic acid preparation is 1～8 hour among the step a, preferred 2～6 hours.
The reaction pressure of peroxycarboxylic acid preparation is 1～101.3kPa among the step a, preferred 10～40kPa.
The stirred-tank reactor of band outer circulation heat-exchange system is adopted in the reaction of peroxycarboxylic acid and pimelinketone among the step b, and its reaction heat removes through the interchanger in the outer circulation heat-exchange system.
Feed way among the step b is that the aqueous peroxycarboxylic acid solution is added in the pimelinketone that is heated to temperature of reaction in advance.
The mol ratio of pimelinketone and peroxycarboxylic acid is 1.01～1.5 among the step b, preferred 1.1～1.3.
The temperature of reaction of 6-caprolactone preparation is 10～90 ℃ among the step b, preferred 30～70 ℃.
The reaction times of 6-caprolactone preparation is 1～8 hour among the step b, preferred 2～6 hours.
Rectifying among the step c is operated under vacuum, and pressure is 0.1～50kPa, preferred 1～20kPa.
The reboiler of rectifying tower is a thin-film evaporator among the step c.
The invention effect
Adopted solid acid catalyst in the process owing to preparing at peroxycarboxylic acid; And after the reaction solid acid catalyst is separated with the aqueous peroxycarboxylic acid solution; Therefore do not contain acid catalyst among the aqueous peroxycarboxylic acid solution who draws, the impurity that generates when reacting with pimelinketone is few, and the contriver also carries out rectification and purification with 6-caprolactone solution through 4 rectifying tower through well-designed; Each composition is carried out round-robin effectively to be utilized; Save material and cost, not only finally can obtain content greater than 99.8% 6-caprolactone, and help industrial applications more.Technology of the present invention has also changed technician in the past and has been confined to guarantee that by adopting the strong acid type catalyzer to be converted into the conventional thought of weak-type catalyzer 6-caprolactone avoids the interference of catalyzer in the later stage of purifying.
In addition, adopted the outer circulation interchanger in the process, improved the exchange capability of heat of this process greatly, temperature of reaction can be controlled steadily owing to preparing at 6-caprolactone.
The more important thing is that the present invention has adopted the excessive mode of pimelinketone in the reaction of peroxycarboxylic acid oxidation pimelinketone; Therefore it is extremely low to be input to peroxycarboxylic acid concentration contained in the material of distillation system; The distillation system appearance is reduced by the possibility of the safety-problems of superoxide initiation greatly, suitability for industrialized production is had extremely important meaning.
Description of drawings
Accompanying drawing is the preparation flow figure of an embodiment; It comprises a preparation aqueous peroxycarboxylic acid solution's step; The step of a preparation 6-caprolactone solution and the step of a purification 6-caprolactone, this schema can be in order to embodiment of the present invention, and R1 is the stirred reactor that has a rectifying tower among the figure; R2 is the reactor drum that band stirs, and A, B, C, D are rectifying tower.Being followed successively by of material in each pipeline:
Pipe 1-ydrogen peroxide 50; Pipe 2-organic carboxyl acid and organic solvent; Pipe 3-reaction waste; Pipe 4-aqueous peroxycarboxylic acid solution; Pipe 5-pimelinketone; Pipe 6-6-caprolactone solution; Pipe 7-A tower distillate; Pipe 8-A tower bottoms; Pipe 9-B tower distillate; Pipe 10-B tower bottoms; Pipe 11-C tower distillate; Pipe 12-C tower bottoms; Pipe 13-6-caprolactone; Pipe 14-D tower bottoms.
Embodiment
Describe main points of the present invention below in detail.
At first; Under solid acid catalysis, in organic solvent, make the aqueous peroxycarboxylic acid solution with the hydrogen peroxide oxidation organic carboxyl acid; Wherein hydrogen peroxide preferably provides with the form of the aqueous solution that contains 30～70% (weight) hydrogen peroxide; The mass ratio of solid acid catalyst and hydrogen peroxide is 0.01～1, and the mol ratio of hydrogen peroxide and organic carboxyl acid is 0.1～1, and the mol ratio of organic solvent and organic carboxyl acid is 0.1～10.
In the above-mentioned aqueous peroxycarboxylic acid solution's of preparation process; Utilize organic solvent and water azeotropic character, organic solvent and water are distilled from cat head, will introduce subsider by the distillate of condenser condenses; Make it to separate into organic phase and water; Only with organic phase reflux to rectifying tower, and water is drained, carry out continuously the distillate of azeotropic dehydration in introducing subsider when no longer containing water basically till.
In the above-mentioned aqueous peroxycarboxylic acid solution's of preparation process, reaction pressure can change according to the composition and the selected temperature of reaction system.Preferably under the absolute pressure of 1～101.3kPa, react, the temperature of reaction of corresponding peroxycarboxylic acid preparation is 10～90 ℃, and the reaction times is 1～8 hour.Among the aqueous peroxycarboxylic acid solution who makes, the content of peroxycarboxylic acid is 5～45% (weight) preferably, and hydrogen peroxide is less than 0.5% (weight), and organic carboxyl acid is 10～80% (weight), and other is an organic solvent.
Second step; Above-mentioned aqueous peroxycarboxylic acid solution is added to a heating in advance (or cooling) in the reactive system that pimelinketone is housed of temperature of reaction; And the used pimelinketone and the mol ratio of peroxycarboxylic acid are 1.01～1.5; Range of reaction temperature is 10～90 ℃, and reaction time range is 1～8 hour, and it is stable that the mode that the cycle heat exchange device removes beyond the thermal recovery that wherein produces in the reaction process is kept temperature of reaction.
The 3rd step, 6-caprolactone solution is carried out rectifying through 4 rectifying tower, 6-caprolactone solution gets into tower A; Distillate organic solvent and a small amount of organic carboxyl acid from cat head, tower bottoms gets into tower B, distillates organic carboxyl acid and pimelinketone from cat head; Distillate gets into tower C again, distillates organic carboxyl acid from cat head, and the tower still obtains pimelinketone; Tower B still liquid gets into tower D, distillates highly purified 6-caprolactone from cat head, and the liquid that contains high-boiling-point impurity is discharged from the tower still.In order to suppress the pyrolysis of 6-caprolactone, preferably in 1～50kPa (absolute pressure) operation down.Tower still reboiler is preferably selected thin-film evaporator for use, to reduce the polymerization of caprolactone.
According to preparation method of the present invention; The good reproducibility of preparation 6-caprolactone; Productive rate is high, and is promptly about 99% based on the transformation efficiency of hydrogen peroxide used in the oxidizing reaction, based on the selectivity of used up pimelinketone greater than 99%; Greater than 99%, thereby can only be contained the 6-caprolactone of minute quantity by product based on the selectivity of used up peroxycarboxylic acid.
Embodiment
Embodiment 1
The preparation of peracetic acid soln
Be 2m earlier with the 100kg perfluorinated sulfonic resin volume of packing into
3Reactor drum R1 in, again from R1 packed 600kg acetate, 440kg ETHYLE ACETATE and 1kg tributyl phosphate into by input tube 2.
This reactor drum is with the distillation tower of adorning filler and the reflux exchanger that has sedimentation tank.(absolute pressure) stirs this solution about 20kPa, with about steam heating to 40 ℃, is that the aqueous hydrogen peroxide solution of 220kg 50% (weight) adds in the R1 through pipeline 1 with total amount.The temperature of control R1 is about 40～45 ℃, will be in reflux exchanger by the organic phase reflux in the heterogeneous azeotrope the cryogenic system condensation under to R1, water from manage 3 drain continuously and through the recovery of organic solvent retrieving arrangement wherein organic solvent and be back to R1.Acetate and hydrogen peroxide are reacted to always and can separate basically in the sedimentation tank after the water, just stop reactor heating R1, and termination reaction.So, make the 1080kg peracetic acid soln.Count reaction needed 3 hours during from the adding hydrogen peroxide.
The composition (weight %) of the peracetic acid soln that does not contain perfluorinated sulfonic resin that obtains from reactor drum 1 bottom is: ETHYLE ACETATE 39.8%, and acetate 38.6%, Peracetic Acid 21.5%, hydrogen peroxide is less than 0.1%.The transformation efficiency that calculates hydrogen peroxide is greater than 99.0%, and the selectivity of Peracetic Acid is 95.4%.
The preparation of 6-caprolactone solution
Next, the above-mentioned peracetic acid soln that makes being equipped with the 320kg pimelinketone through input tube 4 with certain speed input in advance and being heated to 40 ℃ volume is 2m
3Reactor drum R2 in, this reactor drum is equipped with reflux exchanger (not shown) and an outer circulation interchanger, is convenient to control reaction temperature.
From adding the temperature that Peracetic Acid begins just to keep it is 40 ℃, reacts after 3 hours mixture to be cooled to room temperature, makes the 6-caprolactone solution of 1400kg.The 6-caprolactone solution that makes has following composition (weight %): ETHYLE ACETATE 30.7%; Acetate 42.7%, pimelinketone 1.8%, 6-caprolactone 24.5%; Peracetic Acid 0.2%; Calculating the pimelinketone transformation efficiency is 92.1%, and the Peracetic Acid transformation efficiency is 98.8%, and the 6-caprolactone selectivity is 99.8%.
The purification of 6-caprolactone solution
This 6-caprolactone solution is imported among the distillation tower A with the speed of 280kg/h through input tube 6 continuously; This tower is operated under the 20kPa absolute pressure; Low boiling component is discharged with the speed of 88kg/h from vent pipe 7; Reflux simultaneously, and the speed with 192kg/h is input to the tower B through managing 8 from tower A bottom with still liquid with 0.25 reflux ratio; Tower B operates under the 1kPa absolute pressure, and low boiling component is inputed to tower C from vent pipe 9 with the speed of 123kg/h, reflux with 0.5 reflux ratio simultaneously, and the speed with 69kg/h is input to the tower D through managing 10 from tower B bottom with still liquid.Tower D operates under the 1kPa absolute pressure, and cat head distillates high-purity 6-caprolactone with the speed of 68kg/h, refluxes with 2.5 reflux ratio simultaneously, and the tower still is discharged a small amount of raffinate; The distilled material is transported to the tower C from tower B top, and reflux ratio 1 is discharged from vent pipe 11 low boiling component with the speed of 118kg/h, and still liquid is discharged with the speed of 5kg/h from vent pipe 12.Wherein the reboiler of tower B and tower D is thin-film evaporator.
Using the purity of the 6-caprolactone of this methodology acquisition is 99.9% (weight).
The preparation of Perpropionic Acid solution
Be 2m with 100kg strong acidic ion resin (D001 type, the Changsha Da Yu chemical industry ltd produces) volume of packing in advance
3Reactor drum R1 in, again from R1 packed 600kg propionic acid, 400kg ethyl propionate and 1kg tributyl phosphate into by input tube 2.(absolute pressure) stirs this solution about 10kPa, with about steam heating to 50 ℃, is that the aqueous hydrogen peroxide solution of 220kg 50% (weight) adds in the R1 through pipeline 1 with total amount.The temperature of control R1 is about 50～55 ℃, will be in reflux exchanger by the organic phase reflux in the heterogeneous azeotrope the cryogenic system condensation under to R1, water from manage 3 drain continuously and through the recovery of organic solvent retrieving arrangement wherein organic solvent and be back to R1.Propionic acid and hydrogen peroxide are reacted to always and can separate basically in the sedimentation tank after the water, just stop reactor heating R1, and termination reaction.So, make 1050kg Perpropionic Acid solution.Count reaction needed 4 hours during from the adding hydrogen peroxide.
The composition (weight %) of the Perpropionic Acid solution that does not contain ion exchange resin that obtains from reactor drum 1 bottom is: ethyl propionate 38.1%, and propionic acid 35.6%, Perpropionic Acid 26.2%, hydrogen peroxide is less than 0.1%.The transformation efficiency that calculates hydrogen peroxide is 99.0%, and the selectivity of Perpropionic Acid is 95.4%.
The preparation of 6-caprolactone solution
Next, the above-mentioned Perpropionic Acid solution that makes being equipped with the 320kg pimelinketone through input tube 4 with certain speed input in advance and being heated to 50 ℃ volume is 2m
3Reactor drum R2 in, this reactor drum is equipped with reflux exchanger (not shown) and an outer circulation interchanger, is convenient to control reaction temperature.
From adding the temperature that Perpropionic Acid begins just to keep it is 50 ℃, reacts after 3 hours mixture to be cooled to room temperature, makes the 6-caprolactone solution of 1370kg.The 6-caprolactone solution that makes has following composition (weight %): ethyl propionate 29.2%; Propionic acid 43.6%, pimelinketone 1.7%, 6-caprolactone 25.1%; Perpropionic Acid 0.2%; Calculating the pimelinketone transformation efficiency is 92.7%, and the Perpropionic Acid transformation efficiency is 99.0%, and the 6-caprolactone selectivity is 99.6%.
The purification of 6-caprolactone solution
This 6-caprolactone solution is imported among the distillation tower A with the speed of 274kg/h through input tube 6 continuously; This tower is operated under the 10kPa absolute pressure; Low boiling component is discharged with the speed of 82kg/h from vent pipe 7; Reflux simultaneously, and the speed with 192kg/h is input to the tower B through managing 8 from tower A bottom with still liquid with 0.25 reflux ratio; Tower B operates under the 1kPa absolute pressure, and low boiling component is inputed to tower C from vent pipe 9 with the speed of 123kg/h, reflux with 0.5 reflux ratio simultaneously, and the speed with 69kg/h is input to the tower D through managing 10 from tower B bottom with still liquid.Tower D operates under the 1kPa absolute pressure, and cat head distillates high-purity 6-caprolactone with the speed of 68kg/h, refluxes with 2.5 reflux ratio simultaneously, and the tower still is discharged a small amount of raffinate; The distilled material is transported to the tower C from tower B top, and reflux ratio 1.5 is discharged from vent pipe 11 low boiling component with the speed of 116kg/h, and still liquid is discharged with the speed of 7kg/h from vent pipe 12.Wherein the reboiler of tower B and tower D is thin-film evaporator.
Using the purity of the 6-caprolactone of this methodology acquisition is 99.9% (weight).
Claims (18)
1. method for preparing 6-caprolactone may further comprise the steps:
A. in the presence of solid acid catalyst; In the stirred autoclave of band rectifying tower, contain the mixing solutions of organic carboxyl acid and organic solvent with hydrogen peroxide oxidation; Mode through azeotropic distillation distills the water that the water of bringing in the superoxol and reaction process produce from cat head simultaneously, obtains containing the aqueous peroxycarboxylic acid solution of organic solvent from the tower still;
B. will add to the pimelinketone from the aqueous peroxycarboxylic acid solution that step a obtains and react, and make pimelinketone excessive, obtain 6-caprolactone solution;
C. will carry out rectifying through 4 rectifying tower from the 6-caprolactone solution that step b obtains, 6-caprolactone solution gets into tower A, distillates organic solvent and part organic carboxyl acid from cat head; Tower bottoms gets into tower B, distillates organic carboxyl acid and pimelinketone from cat head, and distillate gets into tower C again; Distillate organic carboxyl acid from cat head, the tower still obtains pimelinketone, and tower B still liquid gets into tower D; Distillate 6-caprolactone from cat head, discharge from the tower still than the impurity that 6-caprolactone boiling point is high;
Employed solid acid catalyst is acidic cation-exchange resin, perfluorinated sulfonic resin, molecular sieve, immobilized sulfuric acid, immobilized phosphoric acid or immobilized boric acid among the step a.
2. the method in the claim 1, the mass ratio of solid acid catalyst and hydrogen peroxide is 0.01～1 among the step a.
3. the method in the claim 1, wherein organic carboxyl acid is acetate and/or propionic acid.
4. the method in the claim 1, wherein organic solvent is one or more in ETHYLE ACETATE, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, tert.-butyl acetate, ethyl propionate, propyl propionate, isopropyl propionate, ethyl n-butyrate, the ethyl isobutyrate.
5. the method in the claim 1, wherein the mol ratio of organic solvent and organic carboxyl acid is 0.1～10 among the step a.
6. the method in the claim 1, wherein the mol ratio of hydrogen peroxide and organic carboxyl acid is 0.1～1 among the step a.
7. the method in the claim 1, wherein the water from cat head distilled azeotrope is discharged system among the step a, and organic solvent is back in the tower.
8. the method in the claim 1, wherein the solid acid among the step a is stayed in the reaction kettle, from the aqueous peroxycarboxylic acid solution that reaction kettle is drawn, does not contain solid acid catalyst.
9. the method in the claim 1, wherein the temperature of reaction of peroxycarboxylic acid preparation is 10～90 ℃ among the step a.
10. the method in the claim 1, wherein the reaction times of peroxycarboxylic acid preparation is 1～8 hour among the step a.
11. the method in the claim 1, wherein the reaction pressure of peroxycarboxylic acid preparation is 1～101.3kPa among the step a.
12. the method in the claim 1, wherein the feed way among the step b is that the aqueous peroxycarboxylic acid solution is added in the pimelinketone that is heated to temperature of reaction in advance.
13. the method in the claim 1, wherein the mol ratio of pimelinketone and peroxycarboxylic acid is 1.01～1.5 among the step b.
14. the method in the claim 1, wherein the temperature of reaction of 6-caprolactone preparation is 10～90 ℃ among the step b.
15. the method in the claim 1, wherein the reaction times of 6-caprolactone preparation is 1～8 hour among the step b.
16. the method in the claim 1, wherein the stirred-tank reactor of being with the outer circulation heat-exchange system is adopted in the reaction of peroxycarboxylic acid and pimelinketone among the step b, and its reaction heat removes through the interchanger in the outer circulation heat-exchange system.
17. the method in the claim 1, wherein the rectifying among the step c is operated under vacuum, and pressure is 0.1～50kPa.
18. the method in the claim 1, wherein the reboiler of rectifying tower is a thin-film evaporator among the step c.
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| CN103570667A (en) * | 2012-08-09 | 2014-02-12 | 中国石油化工股份有限公司 | Method for continuously preparing epsilon-lactone |
| CN103588747A (en) * | 2012-08-17 | 2014-02-19 | 中国石油化工股份有限公司 | Production method and apparatus for epsilon-caprolactone |
| CN104003972A (en) * | 2014-04-28 | 2014-08-27 | 安徽红太阳新材料有限公司 | Method for preparing caprolactone |
| CN105646433A (en) * | 2014-11-11 | 2016-06-08 | 中国石油化工股份有限公司 | Process for continuous preparation of high purity epsilon-caprolactone |
| CN105646435A (en) * | 2014-11-11 | 2016-06-08 | 中国石油化工股份有限公司 | Process for continuous preparation of high purity epsilon-caprolactone on the basis of anhydrous peroxy isobutyric acid |
| CN106349140A (en) * | 2016-10-26 | 2017-01-25 | 湖南聚仁化工新材料科技有限公司 | Method for preparing anhydrous peroxide organic carboxylic acid solution |
| CN106543132A (en) * | 2016-11-04 | 2017-03-29 | 湖南聚仁化工新材料科技有限公司 | A kind of method for preparing ε caprolactones |
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| CN107163018A (en) * | 2017-06-23 | 2017-09-15 | 中山大学惠州研究院 | A kind of rectificating method of separate epsilon caprolactone |
| CN110183417A (en) * | 2019-04-30 | 2019-08-30 | 武汉理工大学 | A kind of method and device of catalytic reaction rectification continuous production 6-caprolactone |
| CN110204524A (en) * | 2019-06-19 | 2019-09-06 | 黎明化工研究设计院有限责任公司 | A set of caprolactone synthesizer for having temp auto-controlled ability and its application method |
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| CN111763192A (en) * | 2020-07-14 | 2020-10-13 | 湖南泓源石化仓储有限公司 | Method and device for preparing caprolactone |
| CN115812713A (en) * | 2022-11-29 | 2023-03-21 | 湖南聚仁化工新材料科技有限公司 | Method for co-producing peroxycarboxylic acid disinfectant in production process of disinfectant and caprolactone |
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| CN103570667A (en) * | 2012-08-09 | 2014-02-12 | 中国石油化工股份有限公司 | Method for continuously preparing epsilon-lactone |
| CN103570667B (en) * | 2012-08-09 | 2015-01-21 | 中国石油化工股份有限公司 | Method for continuously preparing epsilon-lactone |
| CN103588747A (en) * | 2012-08-17 | 2014-02-19 | 中国石油化工股份有限公司 | Production method and apparatus for epsilon-caprolactone |
| CN103588747B (en) * | 2012-08-17 | 2015-05-20 | 中国石油化工股份有限公司 | Production method and apparatus for epsilon-caprolactone |
| CN104003972A (en) * | 2014-04-28 | 2014-08-27 | 安徽红太阳新材料有限公司 | Method for preparing caprolactone |
| CN105646433A (en) * | 2014-11-11 | 2016-06-08 | 中国石油化工股份有限公司 | Process for continuous preparation of high purity epsilon-caprolactone |
| CN105646435A (en) * | 2014-11-11 | 2016-06-08 | 中国石油化工股份有限公司 | Process for continuous preparation of high purity epsilon-caprolactone on the basis of anhydrous peroxy isobutyric acid |
| WO2017155441A1 (en) * | 2016-03-09 | 2017-09-14 | Perstorp Ab | Production equipment for production of caprolactone |
| WO2017155442A1 (en) * | 2016-03-09 | 2017-09-14 | Perstorp Ab | Production equipment for production of a caprolactone |
| CN106349140A (en) * | 2016-10-26 | 2017-01-25 | 湖南聚仁化工新材料科技有限公司 | Method for preparing anhydrous peroxide organic carboxylic acid solution |
| CN106543132A (en) * | 2016-11-04 | 2017-03-29 | 湖南聚仁化工新材料科技有限公司 | A kind of method for preparing ε caprolactones |
| CN107163018A (en) * | 2017-06-23 | 2017-09-15 | 中山大学惠州研究院 | A kind of rectificating method of separate epsilon caprolactone |
| CN110183417B (en) * | 2019-04-30 | 2022-01-11 | 武汉理工大学 | Method and device for continuously producing epsilon-caprolactone through catalytic reaction and rectification |
| CN110183417A (en) * | 2019-04-30 | 2019-08-30 | 武汉理工大学 | A kind of method and device of catalytic reaction rectification continuous production 6-caprolactone |
| CN110204524A (en) * | 2019-06-19 | 2019-09-06 | 黎明化工研究设计院有限责任公司 | A set of caprolactone synthesizer for having temp auto-controlled ability and its application method |
| CN110204524B (en) * | 2019-06-19 | 2024-06-18 | 黎明化工研究设计院有限责任公司 | Caprolactone synthesis device with automatic temperature control capability and application method thereof |
| CN110878076A (en) * | 2019-12-12 | 2020-03-13 | 河南能源化工集团研究总院有限公司 | Cyclic oxidation method and equipment for preparing epsilon-caprolactone |
| CN111763192B (en) * | 2020-07-14 | 2023-09-12 | 湖南瑞源石化股份有限公司 | Preparation method and device of epsilon-caprolactone |
| CN111763192A (en) * | 2020-07-14 | 2020-10-13 | 湖南泓源石化仓储有限公司 | Method and device for preparing caprolactone |
| CN115812713A (en) * | 2022-11-29 | 2023-03-21 | 湖南聚仁化工新材料科技有限公司 | Method for co-producing peroxycarboxylic acid disinfectant in production process of disinfectant and caprolactone |
| CN115812713B (en) * | 2022-11-29 | 2024-03-29 | 湖南聚仁新材料股份公司 | Method for co-producing peroxycarboxylic acid disinfectant in disinfectant and caprolactone production process |
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