CN105646435A - Process for continuous preparation of high purity epsilon-caprolactone on the basis of anhydrous peroxy isobutyric acid - Google Patents
Process for continuous preparation of high purity epsilon-caprolactone on the basis of anhydrous peroxy isobutyric acid Download PDFInfo
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Abstract
The present invention discloses a process for continuous preparation of high purity epsilon-caprolactone on the basis of anhydrous peroxy isobutyric acid, according to the process, a reaction and separation integrated apparatus is used for continuous preparation and separation of peroxy isobutyric acid and epsilon-caprolactone, wherein the reaction and separation integrated apparatus comprises a catalytic reaction rectifying column, a reaction rectifying column, a stirring reactor and a rectifying column which are in turn connected, and the process is as follows: iso-butyric acid and hydrogen peroxide are introduced into the catalytic reaction rectifying column for oxidation reaction to separate water under catalysis of strong acid cation exchange resin, the peroxy isobutyric acid produced by the reaction enters the reaction rectifying column, and a crude epsilon-caprolactone solution is obtained by oxidizing reaction of the peroxy isobutyric acid and cyclohexanone entering form the middle part of the reaction rectifying column; and a high yield of the high purity epsilon-caprolactone can be continuously obtained by rectification separation of the crude epsilon-caprolactone solution. The process is simple in operation and mild in reaction conditions, and the product is stable in quality and can meet the industrial production.
Description
Technical field
The present invention relates to a kind of anhydrous technique crossing the oxygen high-purity 6-caprolactone of isopropylformic acid continuous production, belong to 6-caprolactone preparation field.
Background technology
In existing technique, prepared by 6-caprolactone peroxycarboxylic acid peroxyester, and peroxycarboxylic acid used has Peracetic Acid and crosses oxygen propionic acid etc. , in common preparation method, generate the various by product such as hexanodioic acid and 5-hexenoic acid, it is difficult to separation obtains high-purity 6-caprolactone from reaction product.
In Japanese Patent 150681/1982, Japanese Patent 124781/1983 and Chinese patent ZL91109988.3, the one method of refer to, wherein prepare stable 6-caprolactone with the peroxycarboxylic acid peroxyester containing 2��4 carbon atoms, the form that corresponding carboxylic acid and hydrogen peroxide are obtained by reacting " the thick solution of peroxycarboxylic acid " with them under boric acid catalyst exists is used, and under azeotropic conditions continuously except anhydrating. In this kind of ordinary method, because employing weak acid as such in boric acid, when compared with the situation using strongly acidic catalyst, the by product generated in the process preparing 6-caprolactone can lack, but boric acid still can promote that 6-caprolactone open loop generation hydroxycaproic acid, 5-hexenoic acid, propionyloxy ethyl hexanoate, hydroxy ethyl caproate are difficult to the impurity being separated with the oligomer etc. of caprolactone.
Owing to the open loop of caprolactone is had promoter action by water, so should remove totally by de-for water when preparing aqueous peroxycarboxylic acid solution as far as possible, during boric acid catalysis, speed of response is slower, it is generally required to more than 4 hours, being periodical operation in above-mentioned patent, adding of every still material all needs holding time with releasing, intensification and cooling, reduces production efficiency, and the processing parameter such as heating rate and rate of cooling needs to adjust at any time, add control difficulty.
Summary of the invention
Have for the preparation of 6-caprolactone in prior art that side reaction is many, receipts rate is low, separation purification difficult, the defects such as serialization industrial production cannot be realized, it is an object of the invention to the technique being to provide a kind of high yield, continuous production high purity 6-caprolactone, this technological operation is simple, reaction conditions is gentle, constant product quality, meets suitability for industrialized production.
The present invention provides a kind of based on the anhydrous technique crossing the oxygen high-purity 6-caprolactone of isopropylformic acid continuous production, and this technique adopts reaction and separation processes integrated apparatus to carry out the isobutyric preparation of oxygen continuously and be separated the preparation with 6-caprolactone and be separated; Described reaction and separation processes integrated apparatus is made up of the catalytic rectifying column being connected successively, reactive distillation column, stirred autoclave and rectifying tower, and described rectifying tower comprises rectifying I tower and rectifying II tower; When producing continuously, the aqueous solution containing isobutyric organic solution with containing hydrogen peroxide is introduced catalytic rectifying column from catalytic rectifying column top continuously and mixes, under storng-acid cation exchange resin effect, there is catalytic oxidation simultaneously, while carrying out catalytic oxidation, water and organic solvent in reaction mixture are drawn from the tower top of catalytic rectifying column by distillation mode as an azeotrope; The oxygen isopropylformic acid excessively that catalytic oxidation generates and ORGANIC SOLVENT MIXTURES are from introducing reactive distillation tower bottom at the bottom of the tower of catalytic rectifying column, carry out contacting with the pimelinketone entering reactive distillation column in the middle part of reactive distillation column and oxidizing reaction occurs, the oxidation reaction product obtained is introduced stirred autoclave and is reacted further, namely arrives the thick liquid of 6-caprolactone; The thick liquid of gained 6-caprolactone is introduced into rectifying I column distillation and isolates low boiling point organic solvent and isopropylformic acid, then enters rectifying II column distillation and isolate high-boiling-point impurity, obtains the 6-caprolactone that purity is not less than 99.5% continuously; Wherein, containing in isobutyric organic solution adopt organic solvent be one or more in ethyl isobutyrate, trimethylacetic acid methyl esters and trimethylacetic acid second ester.
The technique of the high-purity 6-caprolactone of the continuous production of the present invention also comprises following preferred version:
In preferred scheme, the temperature in catalytic rectifying column is 30��70 DEG C, and pressure is 2��8kPa.
In preferred scheme, the temperature in reactive distillation column is 30��70 DEG C, and pressure is 1��7kPa.
In preferred scheme, stirred autoclave temperature is 30��70 DEG C.
In preferred scheme, control temperature at the bottom of rectifying I tower tower is 100��110 DEG C, and pressure is 0.1��2kPa; Control temperature at the bottom of rectifying II tower tower is 100��110 DEG C, and pressure is 0.1��2kPa.
In preferred scheme, hydrogen peroxide and isobutyric mass ratio are 0.1��0.5:1.
The mol ratio crossing oxygen isopropylformic acid and pimelinketone in preferred scheme is 1.0��1.2:1.
Preferred scheme middle strong acidity Zeo-karb is sulfonate resin and/or perfluorinated sulfonic resin.
Containing organic solvent and isobutyric mass ratio in isobutyric organic solution in preferred scheme is 0.1��5:1.
In preferred scheme, catalytic rectifying column top is provided with division box, and the azeotrope of water and organic solvent is by, after layering, organic solvent is back in catalytic rectifying column.
Preferred scheme isolates organic solvent and isopropylformic acid from rectifying I column overhead; Gained organic solvent and isopropylformic acid return catalytic rectifying column.
Isolating high-purity 6-caprolactone from rectifying II column overhead in preferred scheme, the liquid containing high-boiling-point impurity is discharged from the bottom of tower.
In preferred scheme, catalytic rectifying column and reactive distillation column can arrange one or several series connection respectively, it is possible to make reaction more complete.
Pimelinketone is introduced reactive distillation column by preferred scheme in the middle part of reactive distillation column, effectively carries out fore-distillation before the reaction so that it is in moisture fully eliminate.
The useful effect of the present invention: 6-caprolactone preparation facilities of the prior art and technique are improved by the present invention, oxygen isopropylformic acid solution preparation process excessively have employed storng-acid cation exchange resin as catalyzer, and catalyzer is placed in catalytic rectifying column, water is separated simultaneously, significantly reduced the moisture in oxygen isopropylformic acid solution and catalyst impurities, storng-acid cation exchange resin catalytic efficiency height, the transformation efficiency of hydrogen peroxide is greater than 99%, the selectivity of pimelinketone is greater than 98% by obtained oxygen isopropylformic acid of crossing, finally can obtain the 6-caprolactone that purity is greater than 99.5%.The present invention was by preparing oxygen isopropylformic acid and prepared 6-caprolactone and rectification process combines, effectively realize the continuous prodution of 6-caprolactone, decrease and open shutdown period needed for batch production, improve production efficiency, make technical process steadily controlled, technological parameter fluctuation is little, constant product quality.
Accompanying drawing explanation
The process flow sheet that [Fig. 1] is the present invention: A1 is that centre is equipped with strong acid cation exchange resin catalyst, is filled Packed catalytic rectifying tower up and down; B1 is that centre fills Packed reactive distillation column; B2 is the stirred autoclave of jacketed, and C1, C2 are rectifying tower, and E is luwa evaporator, and V1, V2 are point water return tanks.
Embodiment
Following examples are intended to illustrate further content of the present invention, instead of limit the scope of the invention.
The technical scheme of the present invention is described further by the process flow sheet below in conjunction with the present invention.
First, aqueous hydrogen peroxide solution 1 enters the top of catalytic rectifying column A1 with the carboxylic acid come from distillation system together with organic solvent 2, contact with the material of evaporation at the bottom of the organic solvent of trim the top of column and tower, water wherein and organic solvent azeotropic, steam from tower top through upper section filler, to phase-splitting in point water return tank V1 after condensation, organic phase all refluxes, and aqueous phase 3 is discharged continuously. Hydrogen peroxide and carboxylic acid then down flow through beds, and under storng-acid cation exchange resin catalysis, reaction generates peroxycarboxylic acid, continue down to flow at the bottom of tower after moisture isolated by hypomere filler, finally from obtaining anhydrous aqueous peroxycarboxylic acid solution 4 at the bottom of tower. Reaction pressure can change according to the composition of reaction system and selected temperature.
Subsequently pimelinketone 5 is introduced the middle part of reactive distillation column B1, the minor amount of water azeotropic in pimelinketone is gone out by the organic solvent evaporated at the bottom of tower, anhydrous aqueous peroxycarboxylic acid solution 4 directly introduces at the bottom of tower, react under vacuum condition with pimelinketone at the bottom of tower and generate 6-caprolactone, the heat that reaction process produces is removed by the evaporation of organic solvent, thus can by regulating the pressure of reactive distillation column to control temperature of reaction, materials at bottom of tower 7 introduces the stirred autoclave B2 resume reaction of jacketed, until pimelinketone reacts completely, obtain thick 6-caprolactone solution.
Finally thick 6-caprolactone solution 8 is sent in the middle part of rectifying tower C1, it is separated under vacuo, organic carboxyl acid and organic solvent 9 steam from tower top, return in catalytic rectifying tower A1 together with the solvent 13 added, materials at bottom of tower 10 enters in the middle part of rectifying tower C2, heavy constituent 12 is discharged from the bottom of tower, obtains the 6-caprolactone 11 of high purity from tower top. In order to suppress the polymerization of 6-caprolactone, tower bottom reboiler selects film-type evaporator.
According to the preparation method of the present invention, prepare the repeated good of 6-caprolactone, product rate height, it is possible to obtain the 6-caprolactone of content more than 99.5%.
Embodiment 1
Building experimental installation by accompanying drawing 1, wherein A1 is equipped with catalyzer, B1 and C1, C2 are packing tower, are 500mL there-necked flask at the bottom of each tower, A1 and B1, B2 heating in water bath, C1 and C2 electric mantle heats. Except C2 overhead condensation adopts tap water, other each tower all adopts water at low temperature condensation.
First storng-acid cation exchange resin glasscloth is bundled into sand hill shape, equivalent diameter is about 6��8mm, load the stage casing that diameter is the catalystic rectifying reactor A1 of 45mm, the high about 1000mm of beds, the glass spring filler that 400mm length is respectively housed up and down of catalytic rectifying tower, tower top is equipped with condenser and point water reflux, uses heating in water bath at the bottom of tower.Load 200g ethyl isobutyrate at the bottom of tower in advance, open vacuum pump, regulation system pressure at about 4��6kPa, temperature rising reflux.
Take isopropylformic acid 2000g, ethyl isobutyrate 3000g, 50%H2O21000g adds in 10L bottle, shake even after introduce catalytic rectifying tower upper packing layers and beds boundary with the speed of 300g/h from pipe 1 or 2 with pump, regulate bath temperature and system pressure, make to keep boiling state at about 40��60 DEG C at the bottom of tower, tower top have material steam and maintain ethyl isobutyrate with certain speed backflow, the water separated is expelled in waste water bottle by pipe 3. When liquid level at the bottom of tower is about half left and right, with pump, A1 still liquid is passed through pipe 4 to B1 discharging.
B1 is the glass tower of diameter 34mm, glass filler is housed, 200g ethyl isobutyrate is housed at the bottom of B1 tower and refluxes under vacuo in advance, with pump by A1 still liquid by pipe 4 at the bottom of B1 tower with the speed charging of about 260g/h, with pump, pimelinketone is introduced in the middle part of B1 with the speed of 70g/h by pipe 5 simultaneously, regulating bath temperature and system pressure, make tower top have material to reflux, a small amount of water is discharged from pipe 6. By pipe 7, B1 still liquid is introduced the B2 resume that volume is 2000mL with pump subsequently to react. The pressure of B1 is about 3��5kPa, and the temperature of B1 and B2 all controls at 40��60 DEG C.
When in B2, material reaches the half left and right of still liquid level, by pipe 8, B2 still liquid is introduced the middle part of rectifying tower C1 with pump, electric mantle temperature at the bottom of adjusting tower and C1 pressure tower, column bottom temperature is made to maintain about 100 DEG C, controlling reflux ratio after trim the top of column is about 2, collects the isopropylformic acid steamed and ethyl isobutyrate from pipe 9. Being introduced in the middle part of C2 by pipe 10 with pump when rising to half left and right on C1 still liquid, regulation system pressure and column bottom temperature, set up backflow, control reflux ratio is about 4, collects 6-caprolactone from pipe 11. The pressure-controlling of C1 and C2 is between 0.4��0.8kPa.
Calculate according to product composition, H2O2Transformation efficiency is 99.5%, the transformation efficiency of pimelinketone is 99.7%, being 95.6% based on crossing the isobutyric 6-caprolactone selectivity of oxygen, the 6-caprolactone selectivity based on pimelinketone is 98.2%, and the purity of the 6-caprolactone obtained by this kind of methodology is 99.6% (weight).
Embodiment 2
Experimental installation and the embodiment 1 of embodiment 2 are completely identical, and just raw material and proportioning are different, and the solvent added in advance in each still changes trimethylacetic acid second ester into, and the operational condition of each tower is different.
Take isopropylformic acid 1500g, trimethylacetic acid second ester 3500g, 50%H2O21000g adds in 10L bottle, shake even after introduce from pipe 1 or 2 with the speed of about 300g/h with pump, A1 pressure-controlling at 3��5kPa, still temperature about 40��60 DEG C. Pimelinketone introduces B1, B1 pressure-controlling at about 2��4kPa with the speed of about 70g/h, still temperature about 40��60 DEG C, C1 and C2 pressure-controlling at about 0.5kPa, still temperature about 100��110 DEG C.
Calculate according to product composition, H2O2Transformation efficiency is 99.8%, the transformation efficiency of pimelinketone is 99.5%, being 95.3% based on crossing the isobutyric 6-caprolactone selectivity of oxygen, the 6-caprolactone selectivity based on pimelinketone is 98.8%, and the purity of the 6-caprolactone obtained by this kind of methodology is 99.7% (weight).
Embodiment 3
Experimental installation and the embodiment 1 of embodiment 3 are completely identical, and just raw material and proportioning are different, and the solvent added in advance in each still changes trimethylacetic acid methyl esters into, and the operational condition of each tower is different.
Take isopropylformic acid 2500g, trimethylacetic acid methyl esters 2500g, 50%H2O21000g adds in 10L bottle, shake even after introduce from pipe 1 or 2 with the speed of about 300g/h with pump, A1 pressure-controlling at 6��8kPa, still temperature about 40��60 DEG C. Pimelinketone introduces B1, B1 pressure-controlling at about 5��7kPa with the speed of about 70g/h, still temperature about 40��60 DEG C, C1 and C2 pressure-controlling at about 0.5kPa, still temperature about 100��110 DEG C.
Calculate according to product composition, H2O2Transformation efficiency is 99.3%, the transformation efficiency of pimelinketone is 99.1%, being 95.9% based on crossing the isobutyric 6-caprolactone selectivity of oxygen, the 6-caprolactone selectivity based on pimelinketone is 98.4%, and the purity of the 6-caprolactone obtained by this kind of methodology is 99.8% (weight).
Claims (10)
1. the technique based on the anhydrous oxygen high-purity 6-caprolactone of isopropylformic acid continuous production excessively, it is characterised in that, adopt reaction and separation processes integrated apparatus to carry out the isobutyric preparation of oxygen continuously and be separated the preparation with 6-caprolactone and be separated; Described reaction and separation processes integrated apparatus is made up of the catalytic rectifying column being connected successively, reactive distillation column, stirred autoclave and rectifying tower, and described rectifying tower comprises rectifying I tower and rectifying II tower; When producing continuously, the aqueous solution containing isobutyric organic solution with containing hydrogen peroxide is introduced catalytic rectifying column from catalytic rectifying column top continuously and mixes, under storng-acid cation exchange resin effect, there is catalytic oxidation simultaneously, while carrying out catalytic oxidation, water and organic solvent in reaction mixture are drawn from the tower top of catalytic rectifying column by distillation mode as an azeotrope; The oxygen isopropylformic acid excessively that catalytic oxidation generates and ORGANIC SOLVENT MIXTURES are from introducing reactive distillation tower bottom at the bottom of the tower of catalytic rectifying column, carry out contacting with the pimelinketone entering reactive distillation column in the middle part of reactive distillation column and oxidizing reaction occurs, the oxidation reaction product obtained is introduced stirred autoclave and is reacted further, namely arrives the thick liquid of 6-caprolactone; The thick liquid of gained 6-caprolactone is introduced into rectifying I column distillation and isolates low boiling point organic solvent and isopropylformic acid, then enters rectifying II column distillation and isolate high-boiling-point impurity, obtains the 6-caprolactone that purity is not less than 99.5% continuously; Wherein, containing in isobutyric organic solution adopt organic solvent be one or more in ethyl isobutyrate, trimethylacetic acid methyl esters and trimethylacetic acid second ester.
2. technique as claimed in claim 1, it is characterised in that, the described temperature in catalytic rectifying column is 30��70 DEG C, and pressure is 2��8kPa.
3. technique as claimed in claim 1, it is characterised in that, the described temperature in reactive distillation column is 30��70 DEG C, and pressure is 1��7kPa.
4. technique as claimed in claim 1, it is characterised in that, described stirred autoclave temperature is 30��70 DEG C.
5. technique as claimed in claim 1, it is characterised in that, control temperature at the bottom of described rectifying I tower tower is 100��110 DEG C, and pressure is 0.1��2kPa; Control temperature at the bottom of described rectifying II tower tower is 100��110 DEG C, and pressure is 0.1��2kPa.
6. technique as claimed in claim 1, it is characterised in that, hydrogen peroxide and isobutyric mass ratio are 0.1��0.5:1.
7. technique as claimed in claim 1, it is characterised in that, the mol ratio crossing oxygen isopropylformic acid and pimelinketone is 1.0��1.2:1.
8. technique as claimed in claim 1, it is characterised in that, described storng-acid cation exchange resin is sulfonate resin and/or perfluorinated sulfonic resin.
9. technique as claimed in claim 1, it is characterised in that, described is 0.1��5:1 containing organic solvent in isobutyric organic solution and isobutyric mass ratio.
10. technique as claimed in claim 1, it is characterised in that, catalytic rectifying column top is provided with division box, and the azeotrope of water and organic solvent is by, after layering, organic solvent is back in catalytic rectifying column.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108003130A (en) * | 2017-12-22 | 2018-05-08 | 黎明化工研究设计院有限责任公司 | The integrated apparatus and its application method of a kind of 6-caprolactone synthesis and concentration |
| 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 |
| CN110292786A (en) * | 2019-07-29 | 2019-10-01 | 潍坊益华化工有限公司 | A kind of isooctyl thioglycolate continuous rectification apparatus and technique |
| CN114100527A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Reactive distillation device and method for producing peroxycarboxylic acid |
| WO2022051858A1 (en) * | 2020-09-10 | 2022-03-17 | Datec Coating Corporation | Method and apparatus for the production of performic acid |
| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022051858A1 (en) * | 2020-09-10 | 2022-03-17 | Datec Coating Corporation | Method and apparatus for the production of performic acid |
| 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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Application publication date: 20160608 |