CN108863792B - Comprehensive utilization method of isocoumaene - Google Patents
Comprehensive utilization method of isocoumaene Download PDFInfo
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- CN108863792B CN108863792B CN201810370041.8A CN201810370041A CN108863792B CN 108863792 B CN108863792 B CN 108863792B CN 201810370041 A CN201810370041 A CN 201810370041A CN 108863792 B CN108863792 B CN 108863792B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a comprehensive utilization method of isocitronellene, which removes the peculiar smell of isocitronellene by means of esterification-saponification, converts the isocitronellene into ester or alcohol with certain fragrance, and further improves the yield of esterification reaction by utilizing a reactive distillation technology; the method has the advantages that a reaction rectification mode is adopted, so that a certain byproduct concentration is maintained in the tower, the isomerization reaction is inhibited, the yield of the esterification reaction is improved, the reaction byproducts are reduced, and the burden of three-waste treatment is reduced. The esters obtained from the tower bottom are continuously saponified by adopting an oscillatory flow reactor and then are simply treated to obtain the product, thereby simplifying the post-treatment process. The method not only solves the problems commonly existing in the dihydromyrcene production industry at present, but also recycles waste, reduces production cost, energy consumption and pollution, and improves economic value and social value.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a comprehensive utilization method of isocoumaene.
Background
Isocitronellaene, molecular formula C10H18, CAS number: 65006-04-8, is one of the main by-products in the process of preparing dihydromyrcene by isomerizing pinane. Isocitronellene is an isomer of dihydromyrcene, but its odor is quite contrary to that of dihydromyrcene. Isocitronellene has a strong pungent taste, and a certain amount of isocitronellene is inhaled for a short time, which causes physical discomfort such as dizziness, chest distress, lacrimation, dyspnea, etc. In industry, isocoumarene can not be used as a product directly, or as a raw material or an intermediate. It is of no utility value and can be disposed of only as waste.
At present, the research on isocitronellal is less at home and abroad. The main research direction is to perform esterification reaction on isocitronellene and organic acid to convert the isocitronellene into esters.
In the study of dihydromyrcene cyclization hydration, the national scholars of DouwuBin and Schodder refer to a reaction method of isocoumaene. In particular to a method for preparing corresponding formate by esterification reaction of formic acid and isocoumaene under the catalytic action of an ionic membrane. The resulting formate ester is further saponified to give 3,3, 5-trimethylcycloheptanol. However, the authors' main research direction was focused on the hydration of dihydromyrcene and no deep investigation was made on the esterification of isocarborene. Patent US3546279 discloses a synthesis method of 3,3, 5-trimethylcycloheptanone. In particular to a method for synthesizing 3,3, 5-trimethyl cycloheptanone by taking isocoumaene as a main raw material. It is mentioned in the patent that isocitronellene can react with lower acid under the action of a strongly acidic catalyst to produce corresponding esters. And performing post-treatment such as saponification, oxidation and the like to obtain the target product 3,3, 5-trimethylcycloheptanone. The patent also suggests that the intermediate products of the reaction, such as ester, alcohol, etc., can be used as additives for perfumes for daily use, such as soap, detergent, etc.
The synthesis method can provide some ideas for recycling isocitronellene, but the yield of the final target products of the isocitronellene and the isocitronellene is low. A large amount of isomerization products are generated in the reaction process, which is not in line with the green sustainable development route, and meanwhile, a great amount of byproducts bring certain difficulties to the post-treatment. And is therefore unfavorable from the viewpoint of resource utilization and economy.
Disclosure of Invention
In order to solve the technical problems, the invention provides a new technical scheme for treating and utilizing isocitronellene, which has higher yield, fewer byproducts and more economic and green performance.
A comprehensive utilization method of isocoumaene comprises the following steps:
A. adding isocitronellene into an upper end feed inlet of a reaction rectifying tower, adding organic acid into a lower end feed inlet of the reaction rectifying tower, and carrying out esterification reaction on the isocitronellene and the organic acid in the reaction rectifying tower;
B. separating the product, the byproduct and the redundant reactant generated by the esterification reaction in a tower kettle through a stripping section to obtain a tower kettle product, and separating the product and the redundant reactant in a tower top through a rectifying section to obtain a tower top mixture, wherein the tower top mixture comprises organic acid and the byproduct;
C. and refluxing the mixture at the top of the tower to the reaction rectifying tower for cyclic reaction to obtain isoolefin at the top of the tower.
More preferably, in the method for comprehensively utilizing the isocyclopentadiene, the molar ratio of the isocyclopentadiene to the organic acid is 2: 3-1: 3.
Preferably, in the comprehensive utilization method of the isocoumarene, the theoretical plate number of the reaction rectifying tower is 30-60; the operation pressure is 40 to 100 kPa.
Preferably, the comprehensive utilization method of the isocoumarene further comprises the following steps: adding the tower bottom product and the alkali solution into an oscillatory flow reactor to carry out saponification reaction, standing and layering the reacted mixture, and taking the upper organic phase as corresponding alcohol.
Further preferably, in the comprehensive utilization method of the isocelene, the alkali solution is a sodium hydroxide solution, and the concentration of the alkali solution is 10-50%; the molar ratio of the sodium hydroxide to the ester in the tower bottom product is 1: 1-3: 2; the temperature of the saponification reaction is 70-100 ℃.
Further preferably, in the method for comprehensively utilizing isochrstanene, after the step "standing the reacted mixture for layering, and the upper organic phase is corresponding alcohol", the method further comprises the steps of: and carrying out vacuum rectification operation on the corresponding alcohol to obtain purified alcohol.
Further preferably, in the comprehensive utilization method of the isocoumarene, the theoretical plate number of the vacuum rectification operation is 15-35; the operation pressure is 2-10 kPa; the reflux ratio is 1-5.
Preferably, in the method for comprehensively utilizing the isocoumarene, in the step a, when the used organic acid is not formic acid, a strong acid catalyst is used for the esterification reaction, and the strong acid catalyst is one of sulfuric acid, phosphoric acid, formic acid or solid acid Amberlyst 15.
More preferably, in the comprehensive utilization method of the isocoumarin, the dosage of the strong acid catalyst is 2-5% of the mass of the isocoumarin.
The method for recycling the isocitronellaene provided by the technical scheme of the invention adopts an esterification-saponification method to remove the peculiar smell of the isocitronellaene and convert the isocitronellaene into ester or alcohol with a certain fragrance, and a reaction rectification technology is utilized to further improve the yield of the esterification reaction; the method has the advantages that a reaction rectification mode is adopted, so that a certain byproduct concentration is maintained in the tower, the isomerization reaction is inhibited, the yield of the esterification reaction is improved, the reaction byproducts are reduced, and the burden of three-waste treatment is reduced. The esters obtained from the tower bottom are continuously saponified by adopting an oscillatory flow reactor and then are simply treated to obtain the product, thereby simplifying the post-treatment process. The method not only solves the problems commonly existing in the dihydromyrcene production industry at present, but also recycles waste, reduces production cost, energy consumption and pollution, and improves economic value and social value.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding 98% by mass of sulfuric acid (serving as a strong acid catalyst) and 85% by mass of isocitronene into an upper end feed inlet of a reactive distillation tower, adding 98% by mass of formic acid (with the mass fraction of 98%) in a molar ratio of 1:1.5 to the isocitronene into a lower end feed inlet of the reactive distillation tower, and carrying out esterification reaction on the isocitronene and the formic acid in the reactive distillation tower, wherein the tower top pressure of the reactive distillation tower is 80kPa, and the theoretical plate number is 40;
s2, condensing the steam at the top of the tower through a condenser, collecting an upper-layer isomerization product, completely refluxing formic acid and sending the formic acid to a reaction section for circular reaction, wherein the reflux ratio at the top of the rectifying tower is 10: 1; the tower bottom fraction of the reactive distillation tower is a mixture containing formate obtained by reaction, wherein the concentration of the formate is 93.3%; the yield of the formic ester was 78.5% (based on the starting material).
Example 2
This embodiment is an optimization based on embodiment 1. The method also comprises the following steps after the step S2:
s3, adding formic ether in the tower bottom fraction into an oscillatory flow reactor, mixing with 30% NaOH solution for saponification, wherein the molar ratio of NaOH to formic ether is 1:1.5, and the saponification temperature is 70 ℃;
s4, layering the saponified solution, and taking methanol as an upper organic phase. The saponification yield in this step was 95.3% (based on the ester obtained).
Example 3
This embodiment is an optimization based on embodiment 2. The method also comprises the following steps after the step S4:
s5, storing the upper organic phase (namely methanol) into a temporary storage tank, collecting a certain amount of alcohol liquid in the temporary storage tank, and then sending the liquid in the tank to an intermittent reduced pressure rectifying tower for purification, wherein the pressure at the top of the tower is 4 kPa; the reflux ratio is 5: 1; theoretical plate number of the column 25. A certain amount of front cut fraction is produced, and 99% of alcohol (calculated as mixed alcohol) can be collected at the top of the tower. The final yield of the reaction was 67.5% (based on starting material).
Example 4
This example differs from example 1 in that the strongly acidic catalyst used is phosphoric acid.
Example 5
This example differs from example 1 in that the strongly acidic catalyst used was Amberlyst15, a solid acid.
Example 6
This example is different from example 1 in that a strong acid catalyst is not additionally added from the upper end feed inlet of the reactive distillation column, that is, in different examples, as long as the organic acid reactant used is formic acid, the strong acid catalyst may be added, or the strong acid catalyst may not be added, and the reactant formic acid itself has a catalytic action.
Example 7
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding isocitronene with the mass fraction of 85% into an upper end feeding hole of a reactive distillation tower, adding formic acid (with the mass fraction of 98%) with the molar ratio of 1:2 to the isocitronene into a lower end feeding hole of the reactive distillation tower, wherein the isocitronene and the formic acid have esterification reaction in the reactive distillation tower, the tower top pressure of the reactive distillation tower is 80kPa, and the theoretical plate number is 55;
s2, condensing the steam at the top of the tower through a condenser, collecting an upper-layer isomerization product, completely refluxing formic acid and sending the formic acid to a reaction section for circular reaction, wherein the reflux ratio at the top of the rectifying tower is 15: 1; the tower bottom fraction of the reactive distillation tower is a mixture containing formate obtained by reaction, wherein the concentration of the formate is 92.7%; the yield of the formic ester was 77.3% (based on the starting material).
S3, adding formic ether in the tower bottom fraction into an oscillatory flow reactor, mixing with 30% NaOH solution for saponification, wherein the molar ratio of NaOH to formic ether is 1:2, and the saponification temperature is 70 ℃;
s4, layering the saponified solution, and taking methanol as an upper organic phase. The saponification yield in this step was 95.3% (based on the ester obtained).
S5, after collecting a certain amount of alcohol liquid in the temporary storage tank, sending the liquid in the tank to an intermittent reduced pressure rectifying tower for purification, wherein the pressure at the top of the tower is 4 kPa; the reflux ratio is 5: 1; theoretical plate number of the column 25. A certain amount of front cut fraction is produced, and 99% of alcohol (calculated as mixed alcohol) can be collected at the top of the tower. The final yield of the reaction was 66.5% (based on starting material).
Example 8
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding isocitronellene with the mass fraction of 85% into an upper end feeding hole of a reactive distillation tower, adding formic acid (with the mass fraction of 98%) with the molar ratio of 1:2.5 to the isocitronellene into a lower end feeding hole of the reactive distillation tower, wherein the isocitronellene and the formic acid have esterification reaction in the reactive distillation tower, the tower top pressure of the reactive distillation tower is 90kPa, and the number of theoretical plates is 55;
s2, condensing the steam at the top of the tower through a condenser, collecting an upper-layer isomerization product, completely refluxing formic acid and sending the formic acid to a reaction section for circular reaction, wherein the reflux ratio at the top of the rectifying tower is 15: 1; the tower bottom fraction of the reactive distillation tower is a mixture containing formate obtained by reaction, wherein the concentration of the formate is 88.5%; the yield of the formic ester was 78.3% (based on the starting material).
S3, adding formic ether in the tower bottom fraction into an oscillatory flow reactor, mixing with 30% NaOH solution for saponification, wherein the molar ratio of NaOH to formic ether is 1:2, and the saponification temperature is 70 ℃;
s4, layering the saponified solution, and taking methanol as an upper organic phase. The saponification yield in this step was 95.3% (based on the ester obtained).
Example 9
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding isocitronene with the mass fraction of 85% into the upper end feed inlet of the reactive distillation column, adding formic acid (with the mass fraction of 98%) with the molar ratio of 1:2.5 to the isocitronene into the lower end feed inlet of the reactive distillation column, and filling the solid acid Amberlyst15 into the reaction section of the reactive distillation column. The isocitronellaene and formic acid are subjected to esterification reaction in a reactive distillation tower, the tower top pressure of the reactive distillation tower is 90kPa, and the number of theoretical plates is 45;
s2, condensing the steam at the top of the tower through a condenser, collecting an upper-layer isomerization product, completely refluxing formic acid and sending the formic acid to a reaction section for circular reaction, wherein the reflux ratio at the top of the rectifying tower is 10: 1; the tower bottom fraction of the reactive distillation tower is a mixture containing formate obtained by reaction, wherein the concentration of the formate is 87.6 percent; the yield of the formic ester was 78.8% (based on the starting material).
10 th embodiment
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, mixing 85% by mass of isocourene and 85% by mass of phosphoric acid, adding the mixture into an upper end feed inlet of a reactive distillation column, adding formic acid (the mass fraction is 98%) in a molar ratio of 1:2.5 with the isocourene into a lower end feed inlet of the reactive distillation column, and carrying out esterification reaction on the isocourene and the formic acid in the reactive distillation column, wherein the tower top pressure of the reactive distillation column is 85kPa, and the theoretical plate number is 55;
s2, condensing the steam at the top of the tower through a condenser, collecting an upper-layer isomerization product, completely refluxing formic acid and sending the formic acid to a reaction section for circular reaction, wherein the reflux ratio at the top of the rectifying tower is 15: 1; the tower bottom fraction of the reactive distillation tower is a mixture containing formate obtained by reaction, wherein the concentration of the formate is 87.6 percent; the yield of the formic ester was 76.8% (based on the starting material).
Example 11
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding 85% by mass of isochrysene and 98% by mass of sulfuric acid into an upper end feed inlet of a reactive distillation column after mixing (the amount of the sulfuric acid is 5% of the isochrysene), adding acetic acid with the molar ratio of 1:2 to the isochrysene into a lower end feed inlet of the reactive distillation column, carrying out esterification reaction on the isochrysene and the acetic acid in the reactive distillation column, wherein the tower top pressure of the reactive distillation column is 90kPa, and the theoretical plate number is 45;
s2, condensing the tower top steam through a condenser, collecting a mixture of acetic acid and an isomerization byproduct at the tower top according to a reflux ratio of 15:1, and recovering the acetic acid by rectification after collection; obtaining a mixture of acetic ester at the bottom of the reactive distillation tower, wherein the concentration of the acetic ester is 93.6%; the yield of acetate was 75.5% (based on starting material).
S3, adding acetate in the tower bottom fraction into an oscillatory flow reactor, mixing with 30% NaOH solution for saponification, wherein the molar ratio of NaOH to formate is 1:1.5, and the saponification temperature is 70 ℃;
s4, layering the saponified solution, and taking the upper organic phase as ethanol. The saponification yield in this step was 96.2% (based on the ester obtained).
S5, sending the obtained upper organic phase (namely ethanol) to an intermittent reduced pressure rectifying tower for purification, wherein the tower top pressure is 4 kPa; the reflux ratio is 3: 1; the number of theoretical plates in the column is 30. A certain amount of front cut fraction is produced, and 99% of alcohol (calculated as mixed alcohol) can be collected at the top of the tower. The final yield of the reaction was 67.5% (based on starting material).
Example 12
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding isocitronene with the mass fraction of 85% into an upper end feeding hole of a reactive distillation tower, adding formic acid (with the mass fraction of 98%) with the molar ratio of 1:2 to the isocitronene into a lower end feeding hole of the reactive distillation tower, wherein the isocitronene and the formic acid have esterification reaction in the reactive distillation tower, the tower top pressure of the reactive distillation tower is 90kPa, and the theoretical plate number is 55;
s2, condensing the steam at the top of the tower through a condenser, collecting an upper-layer isomerization product, completely refluxing formic acid and sending the formic acid to a reaction section for circular reaction, wherein the reflux ratio at the top of the rectifying tower is 15: 1; the tower bottom fraction of the reactive distillation tower is a mixture containing formate obtained by reaction, wherein the concentration of the formate is 95.7%; the yield of the formic ester was 80.3% (based on the starting material).
S3, sending the formate in the tower bottom fraction to an intermittent reduced pressure rectifying tower for purification, wherein the tower top pressure is controlled at 4 kPa; the reflux ratio is 5: 1; the number of theoretical plates in the column is 30. A certain amount of front cut fraction is produced, and 99% of formic ester (calculated as mixed ester) can be collected at the top of the tower. The final yield of the reaction was 58.3% (calculated as isocitronellane).
Embodiment 13
A comprehensive utilization method of isocoumaene comprises the following steps:
s1, adding 85% by mass of isochrysene and 98% by mass of sulfuric acid into an upper end feed inlet of a reactive distillation column after mixing (the amount of the sulfuric acid is 5% of the isochrysene), adding acetic acid with the molar ratio of 1:2 to the isochrysene into a lower end feed inlet of the reactive distillation column, carrying out esterification reaction on the isochrysene and the acetic acid in the reactive distillation column, and operating the top of the reactive distillation column at normal pressure, wherein the theoretical plate number is 45;
s2, condensing the tower top steam through a condenser, collecting a mixture of acetic acid and an isomerization byproduct at the tower top according to a reflux ratio of 15:1, and recovering the acetic acid by rectification after collection; obtaining a mixture of acetic ester at the bottom of the reactive distillation tower, wherein the concentration of the acetic ester is 93.6%; the yield of acetate was 75.5% (based on starting material).
S3, sending the acetate in the tower bottom fraction to an intermittent reduced pressure rectifying tower for purification, wherein the tower top pressure is 3 kPa; the reflux ratio is 5: 1; the number of theoretical plates in the column is 30. A certain amount of front cut fraction is produced, and 99% of acetic ester (calculated as mixed ester) can be collected at the top of the tower. The final yield of the reaction was 58.3% (calculated as isocitronellane).
Example 14
The present embodiment differs from embodiment 2 in that:
ester obtained in the tower kettle of the reactive distillation tower enters an oscillatory flow reactor to be mixed with alkali liquor for saponification; the alkali liquor is 20 percent NaOH solution; the molar ratio of NaOH to ester is 1: 2; the saponification temperature is 75 ℃; the saponification yield was 96.3% (calculated as ester).
Example 15
This example differs from example 7 in that:
ester obtained in the tower kettle of the reactive distillation tower enters an oscillatory flow reactor to be mixed with alkali liquor for saponification; the alkali liquor is 20 percent NaOH solution; the molar ratio of NaOH to ester is 1: 2; the saponification temperature is 75 ℃; the saponification yield was 95.8% (calculated as ester).
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The comprehensive utilization method of the isocoumaene is characterized by comprising the following steps:
A. adding isocitronellene into an upper end feed inlet of a reaction rectifying tower, adding organic acid into a lower end feed inlet of the reaction rectifying tower, and carrying out esterification reaction on the isocitronellene and the organic acid in the reaction rectifying tower;
B. separating the product, the byproduct and the redundant reactant generated by the esterification reaction in a tower kettle through a stripping section to obtain a tower kettle product, and separating the product and the redundant reactant in a tower top through a rectifying section to obtain a tower top mixture, wherein the tower top mixture comprises organic acid and the byproduct;
C. refluxing the mixture at the top of the tower to the reaction rectifying tower for cyclic reaction to obtain isoolefin at the top of the tower; adding the tower bottom product and an alkali solution into an oscillatory flow reactor to carry out saponification reaction, standing and layering the reacted mixture, wherein the upper organic phase is corresponding alcohol;
in the step A, the using amount molar ratio of the isocoumaene to the organic acid is 2: 3-1: 3;
the number of theoretical plates of the reaction rectifying tower is 30-60; the operation pressure is 40-100 kPa;
the aqueous alkali is a sodium hydroxide solution, and the concentration of the aqueous alkali is 10-50%; the molar ratio of the sodium hydroxide to the ester in the tower bottom product is 1: 1-3: 2; the temperature of the saponification reaction is 70-100 ℃.
2. The method of claim 1, wherein the alcohol is subjected to a rectification under reduced pressure to obtain a purified alcohol.
3. The method for comprehensively utilizing isochrstanene as claimed in claim 2, wherein the number of theoretical plates for the vacuum distillation operation is 15 to 35; the operation pressure is 2-10 kPa; the reflux ratio is 1-5.
4. The method of claim 1, wherein in step a, when the organic acid is not formic acid, the esterification reaction uses a strongly acidic catalyst, and the strongly acidic catalyst is sulfuric acid, phosphoric acid, formic acid, or Amberlyst 15.
5. The method for the comprehensive utilization of isocitronene as claimed in claim 4, wherein the amount of the strongly acidic catalyst used in the method is 2-5% by mass of isocitronene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546279A (en) * | 1967-02-02 | 1970-12-08 | Int Flavors & Fragrances Inc | Preparation of 3,3,5-trimethyl cycloheptanol and esters thereof |
| US4237322A (en) * | 1978-05-12 | 1980-12-02 | Shell Oil Company | Process for preparation of 1,5-dimethylbicyclo[3,2,1]octan-8-ol |
| CN103664528A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing cyclohexanol |
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- 2018-04-24 CN CN201810370041.8A patent/CN108863792B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546279A (en) * | 1967-02-02 | 1970-12-08 | Int Flavors & Fragrances Inc | Preparation of 3,3,5-trimethyl cycloheptanol and esters thereof |
| US4237322A (en) * | 1978-05-12 | 1980-12-02 | Shell Oil Company | Process for preparation of 1,5-dimethylbicyclo[3,2,1]octan-8-ol |
| CN103664528A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing cyclohexanol |
Non-Patent Citations (1)
| Title |
|---|
| 二甲基-1,6-辛二烯的环化水合反应研究;陶武彬等;《林产化学与工业》;19970630;第17卷(第21期);第13-18页 * |
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