CN109721451A - A kind of australene bisabolene isomer prepares the preparation method of limonene - Google Patents
A kind of australene bisabolene isomer prepares the preparation method of limonene Download PDFInfo
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- CN109721451A CN109721451A CN201811569843.8A CN201811569843A CN109721451A CN 109721451 A CN109721451 A CN 109721451A CN 201811569843 A CN201811569843 A CN 201811569843A CN 109721451 A CN109721451 A CN 109721451A
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- limonene
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Abstract
The invention discloses the preparation methods that a kind of australene bisabolene isomer prepares limonene, including following operating procedure: step 1: the reaction raw materials containing australene being placed in reactive distillation column, investment has supported catalyst in reactive distillation column, the supported catalyst includes kernel and the clad that is coated on outside the kernel, the kernel is aluminum oxide nanoparticle, the clad is chlorination iron layer, 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 limonene mother liquor;Step 3: after-fractionating tower will be put by step 2 treated limonene mother liquor, limonene is distilled in the tower top of after-fractionating tower and is separated, the limonene of high-purity is obtained.The preparation method that the australene bisabolene isomer prepares limonene aims to solve the problem that in the method for existing isomerization production limonene there are limonene 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 lemon
The preparation method of lemon alkene.
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 reaction product is limonene, and limonene is monoterpenes compound, and colourless oil liquid has the lemonish fragrance of class, in food
Middle to be widely used as flavors and fragrances additive, existing australene isomerizalion mode mainly uses single catalyst, causes different
Structure product is mainly carried out toward the direction for generating amphene, and the accounting very little of limonene in the reaction product, is unfavorable for limonene
Mass production.
Summary of the invention
For in the method for existing isomerization production limonene there are limonene yield accounting is small, the lower problem of yield,
The invention discloses the preparation method that a kind of australene bisabolene isomer prepares limonene, which can be improved australene bisabolene isomer mistake
To the selectivity of limonene in journey, limonene yield is improved.
The present invention provides the preparation methods that a kind of australene bisabolene isomer prepares limonene, 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 a supported catalyst in reactive distillation column, the supported catalyst be immersed in liquid level that the reaction raw materials are formed it
Under, the supported catalyst includes kernel and the clad that is coated on outside the kernel, and the kernel is aluminium oxide nano
Grain, the clad are chlorination iron layer, and australene catalytic isomerization under the action of supported catalyst is stirred to react 15-20h, obtains
To 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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 3: after-fractionating tower will be put by step 2 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and obtains the limonene of high-purity, the tower bottom discharging of after-fractionating tower be terpinolene, terpineol,
The mixture of longifolene and other impurities.
Further, the supported catalyst preparation method the following steps are included:
Alumina raw material is ground, aluminum oxide nanoparticle is obtained;
By iron chloride stirring and dissolving Yu Shuizhong, aluminum oxide nanoparticle is put into, makes chlorine in such a way that agitating and heating is distilled
Change iron to be precipitated on the surface of aluminum oxide nanoparticle, grinding is dried to precipitate, obtains supported catalyst.
Further, the weight ratio of aluminium oxide and iron chloride is 10-15:1 in the supported catalyst.
Further, in the step 1, the heating temperature to reaction raw materials is 150 DEG C -170 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 normal 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, the aluminium oxide nano coated using chlorination iron layer provided by the invention
Grain is used as catalyst, can effectively guide the isomerization reaction of australene to carry out toward the direction for generating limonene, to improve lemon
Alkene ratio shared in amphene mother liquor, improves the yield of limonene.
Specific embodiment
The invention discloses the preparation method that a kind of australene bisabolene isomer prepares limonene, which can be improved australene
To the selectivity of limonene during bisabolene isomer, limonene 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 limonene, 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 a supported catalyst in reactive distillation column, the supported catalyst be immersed in liquid level that the reaction raw materials are formed it
Under, the supported catalyst includes kernel and the clad that is coated on outside the kernel, and the kernel is aluminium oxide nano
Grain, the clad are chlorination iron layer, and australene catalytic isomerization under the action of supported catalyst is stirred to react 15-20h, obtains
To 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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 3: after-fractionating tower will be put by step 2 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and obtains the limonene of high-purity, the tower bottom discharging of after-fractionating tower be terpinolene, terpineol,
The mixture of longifolene and other impurities.
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, the aluminium oxide nano coated using chlorination iron layer provided by the invention
Grain is used as catalyst, can effectively guide the isomerization reaction of australene to carry out toward the direction for generating limonene, to improve lemon
Alkene ratio shared in amphene mother liquor, the preparation method for improving supported catalyst described in the yield of limonene includes following step
It is rapid:
Alumina raw material is ground, aluminum oxide nanoparticle is obtained;
By iron chloride stirring and dissolving Yu Shuizhong, aluminum oxide nanoparticle is put into, makes chlorine in such a way that agitating and heating is distilled
Change iron to be precipitated on the surface of aluminum oxide nanoparticle, grinding is dried to precipitate, obtains supported catalyst.
The weight ratio of aluminium oxide and iron chloride is 10-15:1 in the supported catalyst.
In the step 1, the heating temperature to reaction raw materials is 150 DEG C -170 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 normal 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 limonene, including following operating procedure:
Step 1: alumina raw material is ground, and obtains aluminum oxide nanoparticle;
By the iron chloride stirring and dissolving Yu Shuizhong of 1 parts by weight, the aluminum oxide nanoparticle of 13 parts by weight is put into, stirring is passed through
Iron chloride is precipitated on the surface of aluminum oxide nanoparticle in the mode of heating distillation, and grinding is dried to precipitate, is born
Carried catalyst.
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 a supported catalyst in reactive distillation column, the supported catalyst be immersed in liquid level that the reaction raw materials are formed it
Under, the supported catalyst includes kernel and the clad that is coated on outside the kernel, and the kernel is aluminium oxide nano
Grain, the clad are chlorination iron layer, and australene catalytic isomerization under the action of supported catalyst is stirred to react 18h, reaction temperature
Degree is 160 DEG C, 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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 4: after-fractionating tower will be put by step 3 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and the limonene of high-purity is obtained, and obtained limonene is labeled as S1, the tower bottom of after-fractionating tower
Discharging is the mixture of terpinolene, terpineol, longifolene and other impurities.
Embodiment 2:
Present embodiment discloses the preparation methods that a kind of australene bisabolene isomer prepares limonene, including following operating procedure:
Step 1: alumina raw material is ground, and obtains aluminum oxide nanoparticle;
By the iron chloride stirring and dissolving Yu Shuizhong of 1 parts by weight, the aluminum oxide nanoparticle of 10 parts by weight is put into, stirring is passed through
Iron chloride is precipitated on the surface of aluminum oxide nanoparticle in the mode of heating distillation, and grinding is dried to precipitate, is born
Carried catalyst.
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 a supported catalyst in reactive distillation column, the supported catalyst be immersed in liquid level that the reaction raw materials are formed it
Under, the supported catalyst includes kernel and the clad that is coated on outside the kernel, and the kernel is aluminium oxide nano
Grain, the clad are chlorination iron layer, and australene catalytic isomerization under the action of supported catalyst is stirred to react 15h, reaction temperature
Degree is 150 DEG C, 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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 4: after-fractionating tower will be put by step 3 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and the limonene of high-purity is obtained, and obtained limonene is labeled as S2, the tower bottom of after-fractionating tower
Discharging is the mixture of terpinolene, terpineol, longifolene and other impurities.
Embodiment 3:
Present embodiment discloses the preparation methods that a kind of australene bisabolene isomer prepares limonene, including following operating procedure:
Step 1: alumina raw material is ground, and obtains aluminum oxide nanoparticle;
By the iron chloride stirring and dissolving Yu Shuizhong of 1 parts by weight, the aluminum oxide nanoparticle of 15 parts by weight is put into, stirring is passed through
Iron chloride is precipitated on the surface of aluminum oxide nanoparticle in the mode of heating distillation, and grinding is dried to precipitate, is born
Carried catalyst.
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 a supported catalyst in reactive distillation column, the supported catalyst be immersed in liquid level that the reaction raw materials are formed it
Under, the supported catalyst includes kernel and the clad that is coated on outside the kernel, and the kernel is aluminium oxide nano
Grain, the clad are chlorination iron layer, and australene catalytic isomerization under the action of supported catalyst is stirred to react 20h, reaction temperature
Degree is 170 DEG C, 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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 4: after-fractionating tower will be put by step 3 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and the limonene of high-purity is obtained, and obtained limonene is labeled as S3, the tower bottom of after-fractionating tower
Discharging is the mixture of terpinolene, terpineol, longifolene and other impurities.
Comparative example 1
This comparative example discloses the preparation method that a kind of australene bisabolene isomer prepares limonene, including following operating procedure:
Step 1: alumina raw material is ground, and obtains aluminum oxide nanoparticle;
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, it is the aluminum oxide nanoparticle and chlorination iron powder of 13:1, the aluminium oxide that investment, which has weight ratio, simultaneously in reactive distillation column
Nano particle and chlorination iron powder are immersed under the liquid level that the reaction raw materials are formed, australene in aluminum oxide nanoparticle and
Catalytic isomerization under the action of chlorination iron powder is stirred to react 18h, and reaction temperature is 160 DEG C, 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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 4: after-fractionating tower will be put by step 3 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and the limonene of high-purity is obtained, and obtained limonene is labeled as D1, the tower bottom of after-fractionating tower
Discharging is the mixture of terpinolene, terpineol, longifolene and other impurities.
Comparative example 2
This comparative example discloses the preparation method that a kind of australene bisabolene isomer prepares limonene, including following operating procedure:
Step 1: alumina raw material is ground, and obtains aluminum oxide nanoparticle;
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 a chlorination iron powder in reactive distillation column, the chlorination iron powder be immersed in liquid level that the reaction raw materials are formed it
Under, australene catalytic isomerization under the action of chlorination iron powder is stirred to react 18h, and reaction temperature is 160 DEG C, obtains amphene mother
Liquid;
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 distill separation, the first destilling tower tower bottom discharging be limonene mother liquor;
Step 4: after-fractionating tower will be put by step 3 treated limonene mother liquor, in the tower of after-fractionating tower
Limonene is distilled on top to be separated, and the limonene of high-purity is obtained, and obtained limonene is labeled as S1, the tower bottom of after-fractionating tower
Discharging is the mixture of terpinolene, terpineol, longifolene and other impurities.
Pattern detection
By product sample D1, D2 obtained by product sample S1, S2, S3 obtained by embodiment 1-3 and comparative example 1-2 into
The weighing of row weight, detection gained limonene account for the ratio of amphene mother liquor.
It is 43% that testing result, which is that gained limonene accounts for the ratio of amphene mother liquor in sample S1,;Gained limonene in sample S2
The ratio for accounting for amphene mother liquor is 40%;It is 46% that gained limonene, which accounts for the ratio of amphene mother liquor, in sample S3;Gained in sample D1
The ratio that limonene accounts for amphene mother liquor is 31%;It is 29% that gained limonene, which accounts for the ratio of amphene mother liquor, in sample D2.
To sum up, the preparation method that a kind of australene bisabolene isomer provided by the invention prepares limonene effectively increases isomerized products
The content of middle limonene is conducive to the yield for improving limonene.
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 (6)
1. the preparation method that a kind of australene bisabolene isomer prepares limonene, 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 supported catalyst, the supported catalyst is immersed under the liquid level that the reaction raw materials are formed, institute
The clad that supported catalyst includes kernel He is coated on outside the kernel is stated, the kernel is aluminum oxide nanoparticle, institute
Stating clad is chlorination iron layer, and australene catalytic isomerization under the action of supported catalyst is stirred to react 15-20h, 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
The tower bottom discharging of alkene distillation separation, the first destilling tower is limonene mother liquor;
Step 3: will put into after-fractionating tower by step 2 treated limonene mother liquor, the tower top of after-fractionating tower will
Limonene distillation separation, obtains the limonene of high-purity, and the tower bottom discharging of after-fractionating tower is terpinolene, terpineol, comes into leaves
The mixture of alkene and other impurities.
2. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares limonene, which is characterized in that described negative
The preparation method of carried catalyst the following steps are included:
Alumina raw material is ground, aluminum oxide nanoparticle is obtained;
By iron chloride stirring and dissolving Yu Shuizhong, aluminum oxide nanoparticle is put into, makes iron chloride in such a way that agitating and heating is distilled
It is precipitated on the surface of aluminum oxide nanoparticle, grinding is dried to precipitate, obtains supported catalyst.
3. the preparation method that a kind of australene bisabolene isomer according to claim 2 prepares limonene, which is characterized in that described negative
The weight ratio of aluminium oxide and iron chloride is 10-15:1 in carried catalyst.
4. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares limonene, which is characterized in that the step
In rapid one, the heating temperature to reaction raw materials is 150 DEG C -170 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.
5. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares limonene, which is characterized in that the step
In rapid one, the air pressure in the reactive distillation column is normal pressure.
6. the preparation method that a kind of australene bisabolene isomer according to claim 1 prepares limonene, 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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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101347740A (en) * | 2008-08-28 | 2009-01-21 | 复旦大学 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
CN102126904A (en) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | Method for isomerizing alpha-pinene |
CN102343277A (en) * | 2011-06-30 | 2012-02-08 | 大连理工大学 | High performance alpha-pinene isomerization catalyst and application thereof |
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 CN201811569843.8A patent/CN109721451A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101347740A (en) * | 2008-08-28 | 2009-01-21 | 复旦大学 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
CN102126904A (en) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | Method for isomerizing alpha-pinene |
CN102343277A (en) * | 2011-06-30 | 2012-02-08 | 大连理工大学 | High performance alpha-pinene isomerization catalyst and application thereof |
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 |
---|
张金升等: "化铁水溶液和氯化亚铁水溶液性能研究", 《山东交通学院学报》 * |
襄凡市教育局教研室编: "蒸发氯化铁溶液能否得到无水氯化铁固体", 《1979年化学竞赛试题解答》 * |
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Application publication date: 20190507 |