CN109970682A - The method of 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil - Google Patents
The method of 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil Download PDFInfo
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- CN109970682A CN109970682A CN201910369963.1A CN201910369963A CN109970682A CN 109970682 A CN109970682 A CN 109970682A CN 201910369963 A CN201910369963 A CN 201910369963A CN 109970682 A CN109970682 A CN 109970682A
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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Abstract
The method that the present invention relates to a kind of to recycle 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, the following steps are included: the cyclohexane oxidation light oil and carbon dioxide, which are carried out addition reaction under addition catalyst effect, obtains the first reaction solution, the fraction containing cyclohexene carbonate is then obtained by rectifying；The fraction containing cyclohexene carbonate is subjected to decarboxylic reaction under decarboxylation catalyst effect and obtains the second reaction solution, 7-oxa-bicyclo[4.1.0 is then obtained by rectifying.This method utilizes carbon dioxide addition and decarboxylation circular response combination rectifying, isolate the 7-oxa-bicyclo[4.1.0 in light oil, avoid the use of halide, halogen is not contained in product yet, without soda acid processing, and the recyclable reuse of carbon dioxide, environmentally protective and cost reduce, application range is more extensive.
Description
Technical field
The present invention relates to light oil technical fields, recycle epoxide ring from cyclohexane oxidation light oil more particularly to one kind
The method of hexane.
Background technique
7-oxa-bicyclo[4.1.0, Cyclohexene oxide are a kind of colourless or weak yellow liquids with fragrance.Epoxy hexamethylene
Alkane is the main original of synthetic pesticide acaricide propargite (2- (4- tert-butyl benzene oxygroup) cyclohexyl -propyl- 2- alkynyl sulfite)
Material, can be used for synthetic surfactant, rubber chemicals etc..Due to there is very active epoxy group in its molecular structure,
A series of compound for generating high added values can be reacted with amine, phenol, alcohol, carboxylic acid etc..It can such as be synthesized using it as raw material high hard
Degree, high temperature resistant, the unsaturated-resin of acid and alkali-resistance and photoactive coating and photosensitive adhesive etc..In addition, it or a kind of dissolution energy
The very strong organic solvent of power, can be used as epoxide resin reactive diluent.The country utilizes cyclohexane oxidation preparing cyclohexanone there are many
Producer, and in its by-product light oil just contain a large amount of 7-oxa-bicyclo[4.1.0, have adequately recycle value.But mesh
Preceding recovery method is usually required using halide, and certain halogen is also contained in the 7-oxa-bicyclo[4.1.0 product of recycling, is limited
Its field applied.
Summary of the invention
Based on this, it is necessary to provide in the new slave cyclohexane oxidation light oil without using halide of one kind and recycle epoxide ring
The method of hexane.
A method of recycling 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, comprising the following steps:
The cyclohexane oxidation light oil and carbon dioxide are carried out to addition reaction under addition catalyst effect and obtain the
Then first reaction solution is carried out rectifying, obtains the fraction containing cyclohexene carbonate by one reaction solution；
The fraction containing cyclohexene carbonate is subjected to decarboxylic reaction under decarboxylation catalyst effect and obtains the second reaction
Then second reaction solution is carried out rectifying, obtains 7-oxa-bicyclo[4.1.0 by liquid.
Method of the invention is anti-first with carbon dioxide and the 7-oxa-bicyclo[4.1.0 progress addition in cyclohexane oxidation light oil
It answers, obtains the higher cyclohexene carbonate of boiling point, the components such as low-boiling n-amyl alcohol, n-hexyl aldehyde are then removed by rectifying, receive
Collection obtains the fraction containing cyclohexene carbonate.Then the fraction containing cyclohexene carbonate is subjected to decarboxylic reaction, makes carbonic acid hexamethylene
Enester is reduced to 7-oxa-bicyclo[4.1.0 and carbon dioxide, then the 7-oxa-bicyclo[4.1.0 product of high-purity can be obtained by rectifying.The party
Method utilizes carbon dioxide addition and decarboxylation circular response combination rectifying, isolates the 7-oxa-bicyclo[4.1.0 in light oil, avoids halogen
The use of compound does not contain halogen in product yet, handles without soda acid, and carbon dioxide is recyclable reuses, environmentally protective
And cost reduces, application range is more extensive.
The condition of the addition reaction in one of the embodiments, are as follows: reacted in carbon dioxide atmosphere, air pressure
For 0.5MPa~10MPa, reaction temperature is 50 DEG C~230 DEG C, and the reaction time is 0.1 hour~25 hours.
The condition of the decarboxylic reaction in one of the embodiments, are as follows: air pressure is -0.09MPa~0.5Mpa, reaction temperature
Degree is 60 DEG C~400 DEG C, mass space velocity 0.1h-1~5h-1。
Described the step of first reaction solution is carried out rectifying includes: by described first in one of the embodiments,
Reaction solution carries out rectifying, and theoretical cam curve is 15 or more, and boiling point is between 150 DEG C~260 DEG C under collection -0.09MPa~0Mpa
Fraction.
Described the step of second reaction solution is carried out rectifying includes: by described second in one of the embodiments,
Reaction solution carries out rectifying, and theoretical cam curve is 30 or more, and fraction of the boiling point between 128 DEG C~130 DEG C is collected under normal pressure.
The addition catalyst is quaternary ammonium salt catalyst, alkali metal salt catalyst and ion in one of the embodiments,
One of liquid catalyst is a variety of.
The decarboxylation catalyst is alkali metal sulphuric acid salt catalyst in one of the embodiments, alkali carbonate is urged
Agent, alkali nitrates catalyst, alkyl imidazole salt catalyst, ionic-liquid catalyst, base metal catalysts and alkali metal
One of oxide catalyst is a variety of.
It further include to the cyclohexane oxidation lightweight in one of the embodiments, before carrying out the addition reaction
The pre-treatment step of oil: carrying out rectifying for the cyclohexane oxidation light oil, and theoretical cam curve is 30 or more, collects and boils under normal pressure
O'clock in 120 DEG C~137 DEG C of fraction.
The mass ratio of the addition catalyst and the cyclohexane oxidation light oil is in one of the embodiments,
(0.05~5): 100.
The mass ratio of the decarboxylation catalyst and the fraction containing cyclohexene carbonate is in one of the embodiments,
(1~60): 100.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The method that 7-oxa-bicyclo[4.1.0 is recycled in the slave cyclohexane oxidation light oil of one embodiment of the invention, includes the following steps
S1~S2:
S1, by cyclohexane oxidation light oil and carbon dioxide, progress addition reaction obtains first under addition catalyst effect
Then first reaction solution is carried out rectifying, obtains the fraction containing cyclohexene carbonate by reaction solution.
S2, by the fraction containing cyclohexene carbonate, progress decarboxylic reaction obtains the second reaction under decarboxylation catalyst effect
Then second reaction solution is carried out rectifying, obtains 7-oxa-bicyclo[4.1.0 by liquid.
Method of the invention is anti-first with carbon dioxide and the 7-oxa-bicyclo[4.1.0 progress addition in cyclohexane oxidation light oil
It answers, obtains the higher cyclohexene carbonate of boiling point, the components such as low-boiling n-amyl alcohol, n-hexyl aldehyde are then removed by rectifying, receive
Collection obtains the fraction containing cyclohexene carbonate.Then the fraction containing cyclohexene carbonate is subjected to decarboxylic reaction, makes carbonic acid hexamethylene
Enester is reduced to 7-oxa-bicyclo[4.1.0 and carbon dioxide, then the 7-oxa-bicyclo[4.1.0 product of high-purity can be obtained by rectifying.The party
Method utilizes carbon dioxide addition and decarboxylation circular response combination rectifying, isolates the 7-oxa-bicyclo[4.1.0 in light oil, avoids halogen
The use of compound does not contain halogen in product yet, handles without soda acid, and carbon dioxide is recyclable reuses, environmentally protective
And cost reduces, application range is more extensive.
In a specific example, the condition of addition reaction are as follows: reacted in carbon dioxide atmosphere, air pressure is
0.5MPa~10MPa, reaction temperature are 50 DEG C~230 DEG C, and the reaction time is 0.1 hour~25 hours.Preferably, air pressure is
1MPa~5MPa, reaction temperature are 100 DEG C~180 DEG C, and addition reaction effect is more preferable.
In a specific example, the condition of decarboxylic reaction are as follows: air pressure is -0.09MPa~0.5Mpa, reaction temperature 60
DEG C~400 DEG C, mass space velocity 0.1h-1~5h-1.Preferably, air pressure be -0.05MPa~0Mpa, reaction temperature be 150 DEG C~
250 DEG C, mass space velocity 0.5h-1~2h-1, can preferably carry out decarboxylic reaction.
It include: that the first reaction solution is subjected to rectifying by the step of the first reaction solution progress rectifying in a specific example,
Theoretical cam curve be 15 or more, discard fraction of the atmospheric boiling point between 100 DEG C~150 DEG C, then collection -0.09MPa~
Fraction of the boiling point between 150 DEG C~260 DEG C under 0Mpa, to can get the carbonic acid containing 70%~99.5% (mass percent)
The fraction of hexamethylene enester is conducive to subsequent recovery and obtains the higher 7-oxa-bicyclo[4.1.0 product of purity.
It include: that the second reaction solution is subjected to rectifying by the step of the second reaction solution progress rectifying in a specific example,
Theoretical cam curve is 30 or more, and fraction of the boiling point between 128 DEG C~130 DEG C is collected under normal pressure, so that it is higher to can get purity
7-oxa-bicyclo[4.1.0 product.
In a specific example, addition catalyst is that quaternary ammonium salt catalyst, alkali metal salt catalyst and ionic liquid are urged
One of agent is a variety of.Specifically, addition catalyst is 4-dimethylaminopyridine, bis- (the fluoroform sulphurs of N- butyl-pyridinium
Acyl) imines ionic liquid, positive tetrabutyl ammonium halide, triethylamine, Tri-n-Propylamine, tri-n-butylamine, ammonium bromide, iodate amine, 18
Alkyl trimethyl ammonium bromide, sodium bromide, potassium iodide and potassium bromide etc..It is appreciated that the selection of addition catalyst is without being limited thereto, it can
It is adjusted as needed.
In a specific example, decarboxylation catalyst is alkali metal sulphuric acid salt catalyst, alkali carbonate catalyst, alkali
Metal nitrate salt catalyst, alkyl imidazole salt catalyst, ionic-liquid catalyst, base metal catalysts and alkali metal oxide are urged
One of agent is a variety of.Specifically, decarboxylation catalyst is potassium carbonate, magnesia, cetyl imidazoles ammonium chloride and/or ten
Dialkyl group pyridine ammonium bromide.It is appreciated that the selection of decarboxylation catalyst is without being limited thereto, can be adjusted as needed.
It further include to the pre- of cyclohexane oxidation light oil before carrying out above-mentioned addition reaction in a specific example
Processing step: cyclohexane oxidation light oil is subjected to rectifying, theoretical cam curve is 30 or more, and boiling point is at 120 DEG C under collection normal pressure
~137 DEG C of fraction.In this way, most of impurity can be removed by the initial gross separation, it is left the impurity such as n-amyl alcohol, n-hexyl aldehyde, from
And the fraction of the 7-oxa-bicyclo[4.1.0 containing 75%~85% (mass percent) is obtained, be so conducive to subsequent reclaimer operation.It can
To understand, according to the specific impure situation of cyclohexane oxidation light oil, which be can be omitted.
In a specific example, the mass ratio of addition catalyst and cyclohexane oxidation light oil is (0.05~5): 100,
Preferably (0.1~0.5): 100, it can preferably carry out addition reaction.
In a specific example, the mass ratio of decarboxylation catalyst and the fraction containing cyclohexene carbonate is (1~60):
100, preferably (5~20): 100.
The following are specific embodiments.
Embodiment 1
Rectifying column by cyclohexane oxidation light oil at 30 pieces of theoretical cam curve carries out rough segmentation, collects boiling point under normal pressure and exists
120 DEG C~137 DEG C of fraction is obtained containing 80% (w/w) 7-oxa-bicyclo[4.1.0 fraction section.It is put into the autoclave of 2L
The above-mentioned fraction for containing 80% (w/w) 7-oxa-bicyclo[4.1.0 of 1200g, 2.5g 4-dimethylaminopyridine (DMAP) use carbon dioxide replacement
2~4 times, continue to be filled with carbon dioxide to pressure to be 4Mpa, control reaction temperature is 160 DEG C~170 DEG C, interval in reaction process
Carbon dioxide is supplemented, 20h is reacted, sampling analysis reaction conversion ratio is 99%, and reaction selectivity 80%, major impurity is hexamethylene
Glycol.Obtained reaction solution is subjected to batch fractionating, 15 pieces of the theoretical cam curve of rectifying column, lower 100 DEG C~150 DEG C of normal pressure go out to contain
The light components such as n-amyl alcohol, n-hexyl aldehyde are collected component of the boiling point at 150 DEG C~260 DEG C under negative pressure -0.09Mpa, are obtained containing 90%
(w/w) fraction of cyclohexene carbonate.Fraction by gained containing 90% (w/w) cyclohexene carbonate carries out decarboxylic reaction, uses
Potassium carbonate makees catalyst, and the mass ratio of catalyst and the fraction containing cyclohexene carbonate is 10:100, and reaction temperature is 240 DEG C,
Reaction pressure is -0.02Mpa, mass space velocity 0.5h-1, reaction conversion ratio 99.5%, reaction selectivity 65% is main miscellaneous
Matter is cyclohexanone.Resulting carbon dioxide is recycled, resulting reaction solution carries out batch fractionating, theoretical number of plates of rectifying tower
30 pieces, atmospheric distillation, which collects fraction of the boiling point between 128 DEG C~130 DEG C, can be obtained 7-oxa-bicyclo[4.1.0 product, and content is
99.9% (mass ratio).
Embodiment 2
Rectifying column by cyclohexane oxidation light oil at 30 pieces of theoretical cam curve carries out rough segmentation, collects boiling point under normal pressure and exists
120 DEG C~137 DEG C of fraction is obtained containing 80% (w/w) 7-oxa-bicyclo[4.1.0 fraction section.It is put into the autoclave of 2L
The above-mentioned fraction for containing 80% (w/w) 7-oxa-bicyclo[4.1.0 of 1200g, bis- (fluoroform sulphonyl) inferior amine salts of 2.5g N- butyl-pyridinium from
Sub- liquid catalyst continues to be filled with carbon dioxide to pressure to be 5Mpa, control reaction temperature is with carbon dioxide replacement 2~4 times
140~150 DEG C, carbon dioxide is intermittently supplemented in reaction process, reacts 22h, and sampling analysis reaction conversion ratio is 99%, reaction choosing
Selecting property 90%, major impurity are cyclohexanediols.Obtained reaction solution is subjected to batch fractionating, the theoretical cam curve 15 of rectifying column
Block, lower 100 DEG C~150 DEG C of normal pressure go out to contain the light components such as n-amyl alcohol, n-hexyl aldehyde, and boiling point is collected under negative pressure -0.09Mpa at 150 DEG C
~260 DEG C of component obtains the fraction containing 92% (w/w) cyclohexene carbonate.Gained is contained into 92% (w/w) cyclohexene carbonate
Fraction carry out decarboxylic reaction, catalyst, catalyst and evaporating containing cyclohexene carbonate are done using cetyl imidazoles ammonium chloride
The mass ratio divided is 5:100, and reaction temperature is 220 DEG C, and reaction pressure is -0.02Mpa, mass space velocity 1h-1, reaction conversion ratio
It is 99.5%, reaction selectivity 92%, major impurity is cyclohexanone.Resulting carbon dioxide is recycled, it is resulting anti-
Liquid is answered to carry out batch fractionating, 30 pieces of theoretical number of plates of rectifying tower, atmospheric distillation collects boiling point evaporating between 128 DEG C~130 DEG C
Divide and 7-oxa-bicyclo[4.1.0 product can be obtained, content is 99.9% (mass ratio).
Embodiment 3
The recovery method of the present embodiment is substantially the same manner as Example 1, and difference is only that the condition of addition reaction are as follows: air pressure is
0.5MPa, reaction temperature are 50 DEG C, and the reaction time is 12 hours, and sampling analysis reaction conversion ratio is 94.55%, reaction selectivity
It is 81.3%.The 7-oxa-bicyclo[4.1.0 product of preparation, content are 99.45% (mass ratio).
Embodiment 4
The recovery method of the present embodiment is substantially the same manner as Example 1, and difference is only that the condition of decarboxylic reaction are as follows: air pressure is
1Mpa, reaction temperature are 200 DEG C, mass space velocity 5h-1, reaction conversion ratio 76.1%, reaction selectivity 79.6%.Preparation
7-oxa-bicyclo[4.1.0 product, content be 99.10% (mass ratio).
Embodiment 5
The recovery method of the present embodiment is substantially the same manner as Example 1, and difference is only that the reaction solution of addition reaction carries out essence
When evaporating, theoretical cam curve 12 collects fraction of the boiling point between 150 DEG C~260 DEG C under normal pressure.The 7-oxa-bicyclo[4.1.0 of preparation produces
Product, content are 99.03% (mass ratio).
Embodiment 6
The recovery method of the present embodiment is substantially the same manner as Example 1, and difference is only that the reaction solution of decarboxylic reaction carries out essence
When evaporating, theoretical cam curve 25, the 7-oxa-bicyclo[4.1.0 product of preparation, content is 99.54% (mass ratio).
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of method for recycling 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, which comprises the following steps:
The cyclohexane oxidation light oil and carbon dioxide are subjected to addition reaction under addition catalyst effect and obtain first instead
Liquid is answered, first reaction solution is then subjected to rectifying, obtains the fraction containing cyclohexene carbonate；
The fraction containing cyclohexene carbonate is subjected to decarboxylic reaction under decarboxylation catalyst effect and obtains the second reaction solution, so
Second reaction solution is subjected to rectifying afterwards, obtains 7-oxa-bicyclo[4.1.0.
2. the method according to claim 1 for recycling 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, which is characterized in that
The condition of the addition reaction are as follows: reacted in carbon dioxide atmosphere, air pressure is 0.5MPa~10MPa, and reaction temperature is
50 DEG C~230 DEG C, the reaction time is 0.1 hour~25 hours.
3. the method according to claim 1 for recycling 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, which is characterized in that
The condition of the decarboxylic reaction are as follows: air pressure is -0.09MPa~0.5Mpa, and reaction temperature is 60 DEG C~400 DEG C, and mass space velocity is
0.1h-1~5h-1。
4. the method according to claim 1 for recycling 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, which is characterized in that
Described the step of first reaction solution is carried out rectifying includes: that first reaction solution is carried out rectifying, and theoretical cam curve is
Fraction of the boiling point between 150 DEG C~260 DEG C under 15 or more, collection -0.09MPa~0Mpa.
5. the method according to claim 1 for recycling 7-oxa-bicyclo[4.1.0 from cyclohexane oxidation light oil, which is characterized in that
Described the step of second reaction solution is carried out rectifying includes: that second reaction solution is carried out rectifying, and theoretical cam curve is
30 or more, fraction of the boiling point between 128 DEG C~130 DEG C is collected under normal pressure.
6. described in any item methods that 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil according to claim 1~5,
It is characterized in that, the addition catalyst is one of quaternary ammonium salt catalyst, alkali metal salt catalyst and ionic-liquid catalyst
Or it is a variety of.
7. described in any item methods that 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil according to claim 1~5,
It is characterized in that, the decarboxylation catalyst is alkali metal sulphuric acid salt catalyst, alkali carbonate catalyst, alkali nitrates are urged
One of agent, alkyl imidazole salt catalyst, ionic-liquid catalyst, base metal catalysts and alkali metal oxide catalyst
Or it is a variety of.
8. described in any item methods that 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil according to claim 1~5,
It is characterized in that, further includes the pre-treatment step to the cyclohexane oxidation light oil: by institute before carrying out the addition reaction
It states cyclohexane oxidation light oil and carries out rectifying, theoretical cam curve is 30 or more, and boiling point is at 120 DEG C~137 DEG C under collection normal pressure
Fraction.
9. described in any item methods that 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil according to claim 1~5,
It is characterized in that, the mass ratio of the addition catalyst and the cyclohexane oxidation light oil is (0.05~5): 100.
10. described in any item methods that 7-oxa-bicyclo[4.1.0 is recycled from cyclohexane oxidation light oil according to claim 1~5,
It is characterized in that, the mass ratio of the decarboxylation catalyst and the fraction containing cyclohexene carbonate is (1~60): 100.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387890A (en) * | 2021-06-17 | 2021-09-14 | 中国科学院过程工程研究所 | Ionic liquid, polyionic liquid and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4911848A (en) * | 1972-05-16 | 1974-02-01 | ||
| JPS5095248A (en) * | 1973-12-25 | 1975-07-29 | ||
| CN101225077A (en) * | 2007-12-14 | 2008-07-23 | 岳阳昌德化工实业有限公司 | Novel ring-opening reaction method for process of recovering cyclohexene oxide from light oil |
| CN103508982A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Method for separation recovery of cyclohexene oxide from cyclohexanone by-product light oil |
| CN108794300A (en) * | 2018-05-18 | 2018-11-13 | 岳阳昌德化工实业有限公司 | The Isolation method of raw material containing ethylene glycol and 1,2- butanediols and the preparation method of epoxy butane |
-
2019
- 2019-05-06 CN CN201910369963.1A patent/CN109970682B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4911848A (en) * | 1972-05-16 | 1974-02-01 | ||
| JPS5095248A (en) * | 1973-12-25 | 1975-07-29 | ||
| CN101225077A (en) * | 2007-12-14 | 2008-07-23 | 岳阳昌德化工实业有限公司 | Novel ring-opening reaction method for process of recovering cyclohexene oxide from light oil |
| CN103508982A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Method for separation recovery of cyclohexene oxide from cyclohexanone by-product light oil |
| CN108794300A (en) * | 2018-05-18 | 2018-11-13 | 岳阳昌德化工实业有限公司 | The Isolation method of raw material containing ethylene glycol and 1,2- butanediols and the preparation method of epoxy butane |
Non-Patent Citations (1)
| Title |
|---|
| 王开云等: "高纯环氧环己烷的精制工艺研究", 《精细化工中间体》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387890A (en) * | 2021-06-17 | 2021-09-14 | 中国科学院过程工程研究所 | Ionic liquid, polyionic liquid and preparation method and application thereof |
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