CN109721468A - A kind of australene bisabolene isomer prepares the preparation method of terpineol - Google Patents
A kind of australene bisabolene isomer prepares the preparation method of terpineol Download PDFInfo
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- CN109721468A CN109721468A CN201811569844.2A CN201811569844A CN109721468A CN 109721468 A CN109721468 A CN 109721468A CN 201811569844 A CN201811569844 A CN 201811569844A CN 109721468 A CN109721468 A CN 109721468A
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- terpineol
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Abstract
The invention discloses the preparation methods that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure: step 1: the reaction raw materials containing australene being placed in reactive distillation column, investment has catalyst in reactive distillation column, the catalyst, which is negative, is loaded with the micropore aluminium silicophosphate molecular sieve of titanium chloride, australene catalytic isomerization under the effect of the catalyst, obtains amphene mother liquor；Step 2: obtained amphene mother liquor is put into the first destilling tower, the tower bottom discharging of the first destilling tower is terpineol mother liquor；Step 3: after-fractionating tower will be put by step 2 treated terpineol mother liquor, terpineol is distilled in the tower top of after-fractionating tower and is separated.The preparation method that the australene bisabolene isomer prepares terpineol aims to solve the problem that in the method for existing isomerization production terpineol there are terpineol yield accounting is small, the lower problem of yield.
Description
Technical field
The present invention relates to australene isomerized products fabricating technology fields, and in particular to a kind of australene bisabolene isomer prepares terpene
The preparation method of product alcohol.
Background technique
Amphene is a kind of important fine chemicals, is widely used in flavors and fragrances, medicine, synthetic rubber, food, coating
With makeup kind, australene isomerizalion is catalyzed generally under acidic catalyst effect and is made.Since australene has special pair
Ring double bond structure, chemical property is more active, thus in isomerization reaction, side reaction is relatively more, and product component is complicated, wherein one
Kind of reaction product is terpineol, and terpineol product has been more than the pervious byproduct for producing amphene, can be used for synthetic rubber,
The raw material of fragrance, also serves as solvent；As the neck such as enamel paint, varnish and various oleo-resins, resin wax, metal drier and solvent
Or, the terpineol product of demand high-quality, existing australene isomerizalion mode mainly uses single catalyst, and isomerization is caused to produce
Object is mainly carried out toward the direction for generating amphene, and the accounting very little of terpineol in the reaction product, is unfavorable for a large amount of of terpineol
Production.
Summary of the invention
For in the method for existing isomerization production terpineol there are terpineol yield accounting is small, the lower problem of yield,
The invention discloses the preparation method that a kind of australene bisabolene isomer prepares terpineol, which can be improved australene bisabolene isomer mistake
To the selectivity of terpineol in journey, terpineol yield is improved.
The present invention provides the preparation methods that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure:
Step 1: the reaction raw materials containing australene are placed in reactive distillation column, are added to the tower reactor of reactive distillation column
Heat, investment has catalyst in reactive distillation column, and the catalyst is immersed under the liquid level that the reaction raw materials are formed, described to urge
Agent, which is negative, is loaded with the micropore aluminium silicophosphate molecular sieve of titanium chloride, and catalytic isomerization, stirring are anti-under the effect of the catalyst for australene
6-9h is answered, amphene mother liquor is obtained；
Step 2: by obtained amphene mother liquor put into the first destilling tower, the tower top of the first destilling tower will be in amphene mother liquor
Amphene, limonene and terpinolene distillation separation, the first destilling tower tower bottom discharging be terpineol mother liquor；
Step 3: after-fractionating tower will be put by step 2 treated terpineol mother liquor, in the tower of after-fractionating tower
Terpineol is distilled on top to be separated, and obtains the terpineol of high-purity, the tower bottom discharging of after-fractionating tower is longifolene.
Further, the catalyst preparation method the following steps are included:
Titanium chloride is dissolved in anhydrous tetrahydro furan and forms titanium chloride solution, micropore aluminium silicophosphate molecular sieve is immersed in
In titanium chloride solution, titanium chloride solution is infiltrated through in micropore aluminium silicophosphate molecular sieve；
Micropore aluminium silicophosphate molecular sieve is taken out and is dried in vacuo, catalyst is obtained.
Further, in the step 1, the heating temperature to reaction raw materials is 110 DEG C -130 DEG C, is led in reaction process
The gas of evaporation is condensed back by the cooling device for crossing reaction distillation top of tower.
Further, in the step 1, the air pressure in the reactive distillation column is 0.5-0.8 standard atmospheric pressure.
Further, in the step 1, reaction raw materials are persistently stirred, mixing speed is 140-200 revs/min
Clock.
The present inventor is by a large amount of experiment discovery, by selecting specific catalyst that can effectively guide australene
The product of the isomerization reaction of alkene generates direction, specifically, using the micropore aluminium silicophosphate provided by the invention for loading and having titanium chloride
Molecular sieve can effectively guide the isomerization reaction of australene to carry out toward the direction for generating terpineol, to improve as catalyst
Terpineol ratio shared in amphene mother liquor, improves the yield of terpineol.
Specific embodiment
The invention discloses the preparation method that a kind of australene bisabolene isomer prepares terpineol, which can be improved australene
To the selectivity of terpineol during bisabolene isomer, terpineol yield is improved.
The technical solution in the present invention will be clearly and completely described below, it is clear that described is only this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
The invention discloses the preparation methods that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure:
Step 1: the reaction raw materials containing australene are placed in reactive distillation column, are added to the tower reactor of reactive distillation column
Heat, investment has catalyst in reactive distillation column, and the catalyst is immersed under the liquid level that the reaction raw materials are formed, described to urge
Agent, which is negative, is loaded with the micropore aluminium silicophosphate molecular sieve of titanium chloride, and catalytic isomerization, stirring are anti-under the effect of the catalyst for australene
6-9h is answered, amphene mother liquor is obtained；
Step 2: by obtained amphene mother liquor put into the first destilling tower, the tower top of the first destilling tower will be in amphene mother liquor
Amphene, limonene and terpinolene distillation separation, the first destilling tower tower bottom discharging be terpineol mother liquor；
Step 3: after-fractionating tower will be put by step 2 treated terpineol mother liquor, in the tower of after-fractionating tower
Terpineol is distilled on top to be separated, and obtains the terpineol of high-purity, the tower bottom discharging of after-fractionating tower is longifolene.
Inventor is by a large amount of experiment discovery, by selecting specific catalyst that can effectively guide the isomery of australene
The product of reaction generates direction, specifically, having the micropore aluminium silicophosphate molecular sieve of titanium chloride to make using provided by the invention load
For catalyst, it can effectively guide the isomerization reaction of australene to carry out toward the direction for generating terpineol, exist to improve terpineol
Shared ratio, improves the yield of terpineol in amphene mother liquor.
The preparation method of the catalyst the following steps are included:
Titanium chloride is dissolved in anhydrous tetrahydro furan and forms titanium chloride solution, micropore aluminium silicophosphate molecular sieve is immersed in
In titanium chloride solution, titanium chloride solution is infiltrated through in micropore aluminium silicophosphate molecular sieve；
Micropore aluminium silicophosphate molecular sieve is taken out and is dried in vacuo, catalyst is obtained.
In the step 1, the heating temperature to reaction raw materials is 110 DEG C -130 DEG C, passes through reaction distillation in reaction process
The gas of evaporation is condensed back by the cooling device of top of tower.
In the step 1, the air pressure in the reactive distillation column is 0.5-0.8 standard atmospheric pressure.
In the step 1, reaction raw materials are persistently stirred, mixing speed is 140-200 revs/min.
It is illustrated below by way of specific embodiment, raw material used in embodiment is commercially available or self-control, in no spy
In the case where different explanation, unit is (kg).
Embodiment 1:
Present embodiment discloses the preparation methods that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure:
Step 1: titanium chloride being dissolved in anhydrous tetrahydro furan and forms titanium chloride solution, by microporous silicon aluminophosphate molecular
Sieve is immersed in titanium chloride solution, and titanium chloride solution infiltrates through in micropore aluminium silicophosphate molecular sieve；
Micropore aluminium silicophosphate molecular sieve is taken out and is dried in vacuo, catalyst is obtained.
Step 2: the reaction raw materials containing australene are placed in reactive distillation column, are added to the tower reactor of reactive distillation column
Heat, investment has catalyst in reactive distillation column, and the catalyst is immersed under the liquid level that the reaction raw materials are formed, described to urge
Agent, which is negative, is loaded with the micropore aluminium silicophosphate molecular sieve of titanium chloride, and catalytic isomerization, stirring are anti-under the effect of the catalyst for australene
8h is answered, reaction temperature is 110 DEG C, and the air pressure in the reactive distillation column is 0.8 standard atmospheric pressure, obtains amphene mother liquor；
Step 3: by obtained amphene mother liquor put into the first destilling tower, the tower top of the first destilling tower will be in amphene mother liquor
Amphene, limonene and terpinolene distillation separation, the first destilling tower tower bottom discharging be terpineol mother liquor；
Step 4: after-fractionating tower will be put by step 3 treated terpineol mother liquor, in the tower of after-fractionating tower
Terpineol is distilled on top to be separated, and the terpineol of high-purity is obtained, and obtained terpineol is labeled as S1, the tower bottom of after-fractionating tower
Discharging is longifolene.
Embodiment 2:
Present embodiment discloses the preparation methods that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure:
Step 1: titanium chloride being dissolved in anhydrous tetrahydro furan and forms titanium chloride solution, by microporous silicon aluminophosphate molecular
Sieve is immersed in titanium chloride solution, and titanium chloride solution infiltrates through in micropore aluminium silicophosphate molecular sieve；
Micropore aluminium silicophosphate molecular sieve is taken out and is dried in vacuo, catalyst is obtained.
Step 2: the reaction raw materials containing australene are placed in reactive distillation column, are added to the tower reactor of reactive distillation column
Heat, investment has catalyst in reactive distillation column, and the catalyst is immersed under the liquid level that the reaction raw materials are formed, described to urge
Agent, which is negative, is loaded with the micropore aluminium silicophosphate molecular sieve of titanium chloride, and catalytic isomerization, stirring are anti-under the effect of the catalyst for australene
9h is answered, reaction temperature is 130 DEG C, and the air pressure in the reactive distillation column is 0.8 standard atmospheric pressure, obtains amphene mother liquor；
Step 3: by obtained amphene mother liquor put into the first destilling tower, the tower top of the first destilling tower will be in amphene mother liquor
Amphene, limonene and terpinolene distillation separation, the first destilling tower tower bottom discharging be terpineol mother liquor；
Step 4: after-fractionating tower will be put by step 3 treated terpineol mother liquor, in the tower of after-fractionating tower
Terpineol is distilled on top to be separated, and the terpineol of high-purity is obtained, and obtained terpineol is labeled as S2, the tower bottom of after-fractionating tower
Discharging is longifolene.
Comparative example 1
This comparative example discloses the preparation method that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure:
Step 1: the reaction raw materials containing australene are placed in reactive distillation column, are added to the tower reactor of reactive distillation column
Heat, investment has catalyst in reactive distillation column, and the catalyst is immersed under the liquid level that the reaction raw materials are formed, described to urge
Agent is micropore aluminium silicophosphate molecular sieve, and australene catalytic isomerization under the effect of the catalyst is stirred to react 8h, reaction temperature is
110 DEG C, the air pressure in the reactive distillation column is 0.8 standard atmospheric pressure, obtains amphene mother liquor；
Step 2: by obtained amphene mother liquor put into the first destilling tower, the tower top of the first destilling tower will be in amphene mother liquor
Amphene, limonene and terpinolene distillation separation, the first destilling tower tower bottom discharging be terpineol mother liquor；
Step 3: after-fractionating tower will be put by step 2 treated terpineol mother liquor, in the tower of after-fractionating tower
Terpineol is distilled on top to be separated, and the terpineol of high-purity is obtained, and obtained terpineol is labeled as D1, the tower bottom of after-fractionating tower
Discharging is longifolene.
Comparative example 2
This comparative example discloses the preparation method that a kind of australene bisabolene isomer prepares terpineol, including following operating procedure:
Step 1: the reaction raw materials containing australene are placed in reactive distillation column, are added to the tower reactor of reactive distillation column
Heat, investment has catalyst in reactive distillation column, and the catalyst is immersed under the liquid level that the reaction raw materials are formed, described to urge
Agent is titanium chloride, and australene catalytic isomerization under the effect of the catalyst is stirred to react 8h, reaction temperature is 110 DEG C, described anti-
Answering the air pressure in destilling tower is 0.8 standard atmospheric pressure, obtains amphene mother liquor；
Step 2: by obtained amphene mother liquor put into the first destilling tower, the tower top of the first destilling tower will be in amphene mother liquor
Amphene, limonene and terpinolene distillation separation, the first destilling tower tower bottom discharging be terpineol mother liquor；
Step 3: after-fractionating tower will be put by step 2 treated terpineol mother liquor, in the tower of after-fractionating tower
Terpineol is distilled on top to be separated, and the terpineol of high-purity is obtained, and obtained terpineol is labeled as D2, the tower bottom of after-fractionating tower
Discharging is longifolene.
Pattern detection
Product sample D1, D2 obtained by product sample S1, S2 obtained by embodiment 1-2 and comparative example 1-2 are carried out
Weight weighing, detection gained terpineol account for the ratio of amphene mother liquor.
It is 19% that testing result, which is that gained terpineol accounts for the ratio of amphene mother liquor in sample S1,；Gained terpineol in sample S2
The ratio for accounting for amphene mother liquor is 21%；It is 12% that gained terpineol, which accounts for the ratio of amphene mother liquor, in sample D1；Gained in sample D2
The ratio that terpineol accounts for amphene mother liquor is 7%.
To sum up, the preparation method that a kind of australene bisabolene isomer provided by the invention prepares terpineol effectively increases isomerized products
The content of middle terpineol is conducive to the yield for improving terpineol.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (5)
1. the preparation method that a kind of australene bisabolene isomer prepares terpineol, which is characterized in that including following operating procedure:
Step 1: the reaction raw materials containing australene are placed in reactive distillation column, are heated to the tower reactor of reactive distillation column, instead
Investment in destilling tower is answered to have catalyst, the catalyst is immersed under the liquid level that the reaction raw materials are formed, the catalyst
It is negative and is loaded with the micropore aluminium silicophosphate molecular sieve of titanium chloride, australene catalytic isomerization under the effect of the catalyst is stirred to react 6-
9h obtains amphene mother liquor；
Step 2: putting into the first destilling tower for obtained amphene mother liquor, the first destilling tower tower top by the camphane in amphene mother liquor
Alkene, limonene and terpinolene distillation separation, the tower bottom discharging of the first destilling tower is terpineol mother liquor；
Step 3: will put into after-fractionating tower by step 2 treated terpineol mother liquor, the tower top of after-fractionating tower will
Terpineol distillation separation obtains the terpineol of high-purity, and the tower bottom discharging of after-fractionating tower is longifolene.
2. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares terpineol, which is characterized in that described to urge
The preparation method of agent the following steps are included:
Titanium chloride is dissolved in anhydrous tetrahydro furan and forms titanium chloride solution, micropore aluminium silicophosphate molecular sieve is immersed in chlorination
In titanium solution, titanium chloride solution is infiltrated through in micropore aluminium silicophosphate molecular sieve；
Micropore aluminium silicophosphate molecular sieve is taken out and is dried in vacuo, catalyst is obtained.
3. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares terpineol, which is characterized in that the step
In rapid one, the heating temperature to reaction raw materials is 110 DEG C -130 DEG C, passes through the cooling dress of reaction distillation top of tower in reaction process
It sets and is condensed back the gas of evaporation.
4. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares terpineol, which is characterized in that the step
In rapid one, the air pressure in the reactive distillation column is 0.5-0.8 standard atmospheric pressure.
5. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares terpineol, which is characterized in that the step
In rapid one, reaction raw materials are persistently stirred, mixing speed is 140-200 revs/min.
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| CN201811569844.2A CN109721468A (en) | 2018-12-21 | 2018-12-21 | A kind of australene bisabolene isomer prepares the preparation method of terpineol |
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| CN201811569844.2A CN109721468A (en) | 2018-12-21 | 2018-12-21 | A kind of australene bisabolene isomer prepares the preparation method of terpineol |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482113A (en) * | 2003-07-16 | 2004-03-17 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN107892640A (en) * | 2017-05-31 | 2018-04-10 | 怀集县长林化工有限责任公司 | A kind of α firpenes isomery prepares the preparation method of amphene |
-
2018
- 2018-12-21 CN CN201811569844.2A patent/CN109721468A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482113A (en) * | 2003-07-16 | 2004-03-17 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN107892640A (en) * | 2017-05-31 | 2018-04-10 | 怀集县长林化工有限责任公司 | A kind of α firpenes isomery prepares the preparation method of amphene |
Non-Patent Citations (2)
| Title |
|---|
| L. E. MANZER等: "Tetrahydrofuran Complexes of Selected Early Transition Metals", 《INORGANIC SYNTHESES》 * |
| 刘悦: "离子液体催化α-蒎烯水合及异构反应的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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