CN108383702A - A method of extracting citronellal from fruit of a cubeb litsea tree hair oil - Google Patents
A method of extracting citronellal from fruit of a cubeb litsea tree hair oil Download PDFInfo
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- CN108383702A CN108383702A CN201711350165.1A CN201711350165A CN108383702A CN 108383702 A CN108383702 A CN 108383702A CN 201711350165 A CN201711350165 A CN 201711350165A CN 108383702 A CN108383702 A CN 108383702A
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Abstract
The invention discloses a kind of methods that citronellal is extracted in hair oil from the fruit of a cubeb litsea tree, include the following steps：(1) fruit of a cubeb litsea tree hair oil is put into reaction vessel, control temperature of reaction system is 5~15 DEG C, and NaHSO is added dropwise3With the aldehyde ketone in the fruit of a cubeb litsea tree hair oil addition reaction occurs for aqueous solution, obtains the solid product insoluble in fruit of a cubeb litsea tree hair oil；(2) step (1) obtained solid product is detached, extractant is added, acid solution is then added dropwise, 68~72 DEG C of back flow reactions are warming up under stirring, after reaction stratification, organic layer is washed, it is dry after, obtain citronellal crude oil；(3) by citronellal crude oil input rectifying column obtained by step (2), point three sections of progress rectifying obtain methyl heptenone, citronellal and citral respectively.This method is easy to operate, at low cost, efficient, product purity is high, and can coproducing methyl heptenone and citral.
Description
Technical field
The present invention relates to citronellal extractive technique fields, and in particular to the side of citronellal is extracted in a kind of hair oil from the fruit of a cubeb litsea tree
Method.
Background technology
Citronellal is a kind of important mono-isolate, the fragrance with strong, fresh, green citrus sample, micro-strip root of Aucklandia lappa Decne.Lemongrass
Aldehyde is widely used in food flavor, prepares citrus and cherry class essence, the low-grade fragrance for detergents of modulation is also served as, as other fragrance
Raw material is also used for other fragrance such as synthesis of hydroxy citronellal and menthol.There are natural extraction and chemical synthesis in the source of citronellal
Two kinds.Since to bring uncertain impurity into more for synthesis citronellal, endangered caused by human body as food flavor unexpected.
Litsea citrate oil has used more than 30 years as food additives, citronellal is contained in litsea citrate oil, and in it
The chemical constituent that portion is contained does not detect there is the substance especially injured to human body.In addition, demand of the people for natural lemon aldehyde
It is increasing, cause more and more fruit of a cubeb litsea tree hair oils (front-end volatiles of litsea citrate oil) to be wasted as byproduct.
Invention content
For the deficiency and defect mentioned in background above technology, the object of the present invention is to provide it is a kind of it is easy to operate,
It is efficient, product purity is high, and can coproducing methyl heptenone and citral the method that citronellal is extracted from fruit of a cubeb litsea tree hair oil.
A method of it extracting citronellal from fruit of a cubeb litsea tree hair oil, includes the following steps：
(1) fruit of a cubeb litsea tree hair oil is put into reaction vessel, control temperature of reaction system is 5~15 DEG C, and NaHSO is added dropwise3Water
With the aldehyde ketone in the fruit of a cubeb litsea tree hair oil addition reaction occurs for solution, obtains the solid product insoluble in fruit of a cubeb litsea tree hair oil；
(2) step (1) obtained solid product is detached, extractant is added, acid solution is then added dropwise, 68 are warming up under stirring
~72 DEG C of back flow reactions, stratification after reaction, organic layer is washed, it is dry after, obtain citronellal crude oil；
(3) by citronellal crude oil input rectifying column obtained by step (2), point three sections of progress rectifying divide three sections of progress rectifying,
Methyl heptenone, citronellal and citral are obtained respectively.
The present invention into fruit of a cubeb litsea tree hair oil by being added dropwise NaHSO3Aqueous solution, and it is 5~15 DEG C to control temperature of reaction system,
Pass through NaHSO3Feature addition reaction is played with the aldehyde ketone in fruit of a cubeb litsea tree hair oil and generates solid intermediate product, by solid intermediate product point
From rear, acid solution is added dropwise and is stirred at reflux reaction, make intermediate product removing sulfonic group, be back to aldehyde ketone, by citronellal and other aldehyde,
Letones are separated from fruit of a cubeb litsea tree hair oil, obtain citronellal crude oil；Then by rectifying, vacuum degree and Ta Nei temperature are controlled
Citronellal, methyl heptenone and citral are isolated from citronellal crude oil.This method is easy to operate, at low cost, efficient, production
Product purity is high, and can coproducing methyl heptenone and citral.Aldehyde ketone and NaHSO in step (1) in fruit of a cubeb litsea tree hair oil3Reaction
In the process, reaction temperature need to be controlled at 5~15 DEG C, side reaction can be caused to increase if reaction temperature is excessively high, will be made the production of citronellal
Rate substantially reduces.
Preferred scheme, in step (3), points three sections carry out a rectifying and specifically refer to, first segment rectifying：Vacuum degree in control tower
For 0.9~1.1MPa, temperature is 45~55 DEG C in tower, collects fraction and obtains methyl heptenone；Second segment rectifying：Vacuum in control tower
It is 0.09~0.11MPa to spend, and temperature is 45~55 DEG C in tower, collects fraction and obtains citronellal；Third section rectifying：Vacuum in control tower
It is 0.09~0.11MPa to spend, and temperature is 70~74 DEG C in tower, collects fraction and obtains citral.By controlling vacuum degree in rectifying column
Within the above range with temperature, Fractional Collections methyl heptenone, citronellal and citral, products therefrom purity are high.
Preferred scheme, in step (3), first segment rectifying the specific steps are：In slow adjusting tower vacuum degree be 0.9~
Rectifying column is heated to 45~55 DEG C with the rate of 1.8~2.2 DEG C/min with conduction oil, rectifying column mouth is made to steam by 1.1MPa
Then vapour keeps 25~35min of infinite reflux, starts to discharge, collect this section of fraction and obtain methyl heptenone, methyl heptenone will go out
Temperature in tower is increased 4~6 DEG C with the rate of 1.8~2.2 DEG C/min when to the greatest extent.
Further preferred scheme, in step (3), first segment rectifying the specific steps are：Vacuum degree in slow adjusting tower
For 1MPa, rectifying column is heated to 50 DEG C with the rate of 2 DEG C/min with conduction oil, so that rectifying column mouth steam is occurred, then keeps
Infinite reflux 30min starts to discharge, and collects this section of fraction and obtains methyl heptenone, when methyl heptenone will go out to the greatest extent with 2 DEG C/
Temperature in tower is increased 5 DEG C by the rate of min.
Preferred scheme, in step (3), second segment rectifying the specific steps are：After waiting for that methyl heptenone has gone out, slowly
Rectifying column is warming up to 45 by vacuum degree with conduction oil to 0.09~0.11MPa with the rate of 1.8~2.2 DEG C/min in adjusting tower
~55 DEG C, rectifying column mouth is made steam occur, then keeps 25~35min of infinite reflux, start to discharge, collect this section of fraction and obtain lemongrass
Temperature in tower is increased 4~6 DEG C by aldehyde when citronellal will go out to the greatest extent with the rate of 1.8~2.2 DEG C/min.
Further preferred scheme, in step (3), second segment rectifying the specific steps are：Wait for that methyl heptenone has gone out it
Afterwards, rectifying column is warming up to 50 DEG C with the rate of 2 DEG C/min with conduction oil, makes essence by vacuum degree to 0.1MPa in slow adjusting tower
It evaporates tower mouth and steam occurs, then keep infinite reflux 30min, start to discharge, collect this section of fraction and obtain citronellal, citronellal will go out
Temperature in tower is increased 5 DEG C with the rate of 2 DEG C/min when to the greatest extent.
Preferred scheme, in step (3), third section rectifying the specific steps are：After waiting for that citronellal has gone out, conduction oil is used
Rectifying column is warming up to 70~74 DEG C with the rate of 1.8~2.2 DEG C/min, rectifying column mouth is made steam occur, then keeps complete and returns
Flow 25~35min, start to discharge, collect this section of fraction and obtain citral, when citral will go out to the greatest extent with 1.8~2.2 DEG C/
Temperature in tower is increased 4~6 DEG C by the rate of min.
Further preferred scheme, in step (3), third section rectifying the specific steps are：After waiting for that citronellal has gone out, use
Rectifying column is warming up to 72 DEG C by conduction oil with the rate of 2 DEG C/min, so that rectifying column mouth steam is occurred, is then kept infinite reflux
30min starts to discharge, and collects this section of fraction and obtains citral, citral will be in tower with the rate of 2 DEG C/min when will going out to the greatest extent
Temperature increases 5 DEG C.
Further preferred scheme, in step (3), vacuum degree is in control tower in first segment rectifying and second segment rectifying
1MPa, temperature is 50 DEG C in control tower, and vacuum degree is 0.1MPa in control tower in third section rectifying, and temperature is 72 DEG C in tower.
Preferred scheme, in step (3), before carrying out first segment rectifying, vacuum degree is 4~6MPa in first adjusting tower,
Temperature is 25~35 DEG C in tower, makes 25~35min of citronellal crude oil boiling in tower, the light component in citronellal crude oil is steamed.
Further preferred scheme, in step (3), before carrying out first segment rectifying, vacuum degree is in first adjusting tower
5MPa, temperature is 30 DEG C in tower, so that citronellal crude oil is boiled 30min, the light component in citronellal crude oil is steamed.
Vacuum degree and temperature in adjusting tower are first passed through before first segment rectifying, and the light component in citronellal crude oil is steamed
Go out, light component is avoided to be mixed into rectifying product, is conducive to the purity for improving methyl heptenone, citronellal and citral product.
Preferred scheme, in step (1), NaHSO3After aqueous solution is added drop-wise in fruit of a cubeb litsea tree hair oil, light yellow crystal is generated,
As dropwise addition NaHSO3When light yellow crystal no longer increases after aqueous solution, stops being added dropwise, reaction solution be filtered, filter residue is through washing
After washing, drying, solid product is obtained.
Further preferred scheme, in step (1), the solvent used in washing operation is that nonpolarity or low pole are organic molten
Agent, any one of the nonpolarity or weakly polar organic solvent in ethyl acetate, petroleum ether, ether, hexamethylene, into one
Step is preferably ether.
Preferred scheme, in step (2), extractant is any one in ethyl acetate, petroleum ether, ether, hexamethylene
Kind, further preferably ether.
Preferred scheme, in step (2), acid solution is the acetic acid solution of mass fraction 10%, and the temperature of reflux is 70 DEG C.
Preferred scheme, in step (1), the temperature control of reaction system is at 10 DEG C, NaHSO3The mass fraction of aqueous solution
It is 25%.
Preferred scheme, in step (2), the drier used in drying process is neutral or faintly acid drier, is selected from nothing
Water magnesium sulfate or anhydrous calcium chloride, further preferably anhydrous magnesium sulfate.
Fruit of a cubeb litsea tree hair oil used in the present invention can be the existing byproduct (inventory obtained by citral abstraction process
Fruit of a cubeb litsea tree hair oil), can also be the fruit of a cubeb litsea tree hair oil being prepared by the following method by fruit of a cubeb litsea tree fresh fruit：
Fruit of a cubeb litsea tree fresh fruit is washed, is placed in alembic, 1.5~2 times of fruit of a cubeb litsea tree weight is added (further preferably
1.5 times) the residual water of flask (last time distillation after, the water that material obtains after filtering, partition losses water using clear water benefit
Fill), it is extracted using volatile oil extractor, obtains Litsea Cubeba oil；
By gained Litsea Cubeba oil be added distilling flask in, vacuumize and distilled, control vacuum degree be 0.09~
0.11MPa, distilling flask top temperature are 45~55 DEG C, collect fraction to get fruit of a cubeb litsea tree hair oil.
Further preferred scheme, control vacuum degree is 0.1MPa when Litsea Cubeba oil is evaporated in vacuo, and controls distilling flask
Top temperature is 50 DEG C.
Further preferred scheme, alembic is using 4~8kg pressure vapor as heating carrier；Reflux in alembic
Amount control is in 125~175L/h.The pressure of vapor is more preferably 6kg, and regurgitant volume is more preferably 150L/h.
Compared with the prior art, the advantages of the present invention are as follows：The present invention first by fruit of a cubeb litsea tree hair oil aldehyde ketone with
NaHSO3Addition reaction is carried out, the solid intermediate product insoluble in oil phase is generated；Then solid intermediate product is made by acid solution
Back reaction occurs and is back to aldehyde ketone, realization isolates substance in aldehyde ketone from fruit of a cubeb litsea tree hair oil, obtains citronellal crude oil；Again by lemongrass
Aldehyde crude oil carries out segmentation rectifying and obtains methyl heptenone, citronellal and citral.The preparation process of the present invention is simple, at low cost, raw
Produce efficient, obtained citronellal purity is up to 98% or more, and can coproduction high added value byproduct methyl heptenone and lemon
Lemon aldehyde.The raw material of the present invention can be the fruit of a cubeb litsea tree hair oil obtained after slightly carrying and distilling by fruit of a cubeb litsea tree fresh fruit, can also be lemon
The fruit of a cubeb litsea tree hair oil byproduct obtained in lemon aldehyde production process solves the waste of fruit of a cubeb litsea tree hair oil and library in current citral production
The problem of depositing.
Description of the drawings
Fig. 1 is the gas chromatographic analysis figure of 1 gained citronellal of the embodiment of the present invention.
Fig. 2 is the data from gas chromatography of citronellal in Fig. 1.
Fig. 3 is the sample photo of 1 gained citronellal of the embodiment of the present invention.
Fig. 4 is the gas chromatographic analysis figure of 1 gained methyl heptenone of the embodiment of the present invention.
Fig. 5 is the data from gas chromatography of methyl heptenone in Fig. 4.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of method that citronellal is extracted from fruit of a cubeb litsea tree hair oil of the present invention, wherein fruit of a cubeb litsea tree hair oil used is grey by mountain
Sub- fresh fruit warp slightly carries and distillation obtains, and specific extracting method is as follows：
(1) fruit of a cubeb litsea tree slightly carries：
The fruit of a cubeb litsea tree fresh fruit picked is cleaned up, fresh fruit 150kg is weighed and is placed in water in alembic, it is grey that mountain is added
The water (225kg) of 1.5 times of sub- fresh fruit weight.Using 4kg pressure vapor as heating carrier, and carried using 1000L is multi-functional
It takes device to extract, adjusts the temperature and steam pressure of water distillation, regurgitant volume is controlled in 150L/h；
After distillation, by the material in distilling flask through filter screen filtration, remaining water is then used as next time in flask
It feeds intake and uses water.Upper layer dry fruit is discharged as byproduct, and Litsea Cubeba oil is released from oil water separator, amounts to 7.75kg.Grease
Water phase in separator and the residual hydration of flask and total 192.3kg, into feeding intake next time.
(2) Litsea Cubeba oil distills
By in the Litsea Cubeba oil 2.0kg input 3L distilling flasks of preparation, the stirring of distilling flask is opened, vacuum is accessed.
Using heat-conducting oil heating；Vacuum pump is adjusted to 5MPa, and conduction oil temperature setting is 30 DEG C, and heating rate is 2 DEG C/min, starts to be discharged
Head；After head has gone out, distilling flask is heated up with 2 DEG C/min, until tower top temperature rises to 50 DEG C, keeps flask and conduction oil
It is temperature-resistant, start to discharge, discharging substance is fruit of a cubeb litsea tree hair oil, amounts to discharging 392g.
(3) fruit of a cubeb litsea tree hair oil is refined
By in gained fruit of a cubeb litsea tree hair oil 392g input 1L three-necked flasks, magneton stirring is added, opens frozen cooling, waits for flask
When temperature drop is to 10 DEG C, the NaHSO that mass fraction is 25% is slowly added dropwise3Aqueous solution generates light yellow crystal immediately, works as dropwise addition
NaHSO3When light yellow crystal no longer increases after aqueous solution, stop being added dropwise, reaction solution is filtered, obtains faint yellow solid crystalline substance
Body；Obtained solid crystal is washed twice through ethyl acetate mashing, 25 DEG C is put into, is dried in -0.95MPa drying boxes, do
Faint yellow solid product 154g is obtained after dry.
(4) solid product essence carries
Gained 154g solid products are added in three-necked flask, put up condensation reflux unit, and connect tail gas absorption.It is added
Then a certain amount of extractant ethyl acetate is added dropwise the acetic acid solution that mass fraction is 10%, opens stirring, and be heated to
70 DEG C of back flow reactions, solid product all dissolve and generate bulk gas discharge, until there is no bubble releasing in three-necked flask,
Stop reaction, system is made to be cooled to room temperature.By reaction solution stratification, organic layer is separated, is washed twice, the anhydrous sulphur of organic layer
Sour magnesium drying, revolving obtain citronellal crude oil 43g.
(5) citronellal crude oil purifies
43g citronellal crude oils are put into rectifying column, adjusting vacuum is 5MPa, adjusts the temperature to 30 DEG C, infinite reflux half is small
When.Light component is drawn clean；Slowly vacuum is adjusted until vacuum gives rectifying column to heat equal to 1MPa, with conduction oil, until rectifying
There is steam in tower mouth, is kept for infinite reflux state half an hour, then starts to discharge, and collects fraction and obtains methyl heptenone, methyl heptenyl
Temperature in tower is increased 5 DEG C with the rate of 2 DEG C/min when ketone will go out to the greatest extent；After waiting for that methyl heptenone has gone out, slowly adjust
Vacuum is saved to 0.1MPa, is heated up with the rate of 2 DEG C/min with conduction oil, until there is steam, is kept for infinite reflux state half an hour,
Then start to discharge, collect fraction and obtain citronellal, with the rate of 2 DEG C/min by temperature liter in tower when citronellal will go out to the greatest extent
It is 5 DEG C high；After waiting for that citronellal has gone out, is heated up with the rate of 2 DEG C/min with conduction oil, until there is steam, keep infinite reflux shape
Then state half an hour starts to discharge, collect fraction and obtain citral.Citronellal yield is 11g, and methyl heptenone yield is 15g, lemon
Lemon aldehyde yield about 1~2g.
Gas chromatographic analysis is carried out to gained citronellal product, analysis condition is：Shimadzu 2010plus gas chromatographs,
Db-5 low pole chromatographic columns, temperature programming are 80~250 DEG C, 10 DEG C of heating per minute.
The chromatography figure of citronellal product is as shown in Figure 1, Fig. 2 is the data from gas chromatography figure in Fig. 1, by Fig. 1 and Fig. 2
As it can be seen that the content of citronellal is 98.37% (corresponding retention time is at 7.449) in the citronellal product that extraction obtains.Gained
The sample photo of citronellal product is as shown in Figure 3.
Gas chromatographic analysis is carried out to gained methyl heptenone, analysis condition is：Shimadzu 2010plus gas chromatographs,
Db-5 low pole chromatographic columns, temperature-rising method are 2 DEG C of the heating per minute of 80-140 DEG C of temperature section, and 140-250 DEG C of temperature section is per minute
10 DEG C of heating.
The chromatography figure of gained methyl heptenone as shown in figure 4, its data from gas chromatography as shown in figure 5, by Fig. 4 and figure
5 as it can be seen that the content of methyl heptenone is 99.19% (corresponding retention time is in the obtained methyl heptenone product of extraction
13.779 place)
Embodiment 2：
A kind of method that citronellal is extracted from fruit of a cubeb litsea tree hair oil of the present invention, wherein fruit of a cubeb litsea tree hair oil used is grey by mountain
Sub- fresh fruit warp slightly carries and distillation obtains, and specific extracting method is as follows：
(1) fruit of a cubeb litsea tree slightly carries：
The fruit of a cubeb litsea tree fresh fruit picked is cleaned up, weighs and fresh fruit 150kg is taken to be placed in water in alembic, mountain is added
The water (225kg) of grey 1.5 times of sub- fresh fruit weight.Using 4kg pressure vapor as heating carrier, and it is multi-functional using 1000L
Extraction element extracts, and adjusts the temperature and steam pressure of water distillation, and regurgitant volume is controlled in 150L/h；
After distillation, by the material in distillation through filter screen filtration, remaining water is then as feeding intake next time in flask
Use water.Upper layer dry fruit is discharged as byproduct, and Litsea Cubeba oil is released from oil water separator, amounts to 7.75kg.Water-oil separating
Water phase in device and the residual hydration of flask and total 192.3kg, into feeding intake next time.
(2) Litsea Cubeba oil distills
By in the Litsea Cubeba oil 2.0kg input 3L distilling flasks of preparation, the stirring of distilling flask is opened, vacuum is accessed.
Using heat-conducting oil heating；Vacuum pump is adjusted to 5MPa, and conduction oil temperature setting is 30 DEG C, and heating rate is 2 DEG C/min, starts to be discharged
Head；After head has gone out, distilling flask is heated up with 2 DEG C/min, until tower top temperature rises to 50 DEG C, keeps flask and conduction oil
It is temperature-resistant, start to discharge, discharging substance is fruit of a cubeb litsea tree hair oil, amounts to discharging 403g.
(3) fruit of a cubeb litsea tree hair oil is refined
By in gained fruit of a cubeb litsea tree hair oil 403g input 1L three-necked flasks, magneton stirring is added, opens frozen cooling, waits for flask
When temperature drop is to 15 DEG C, the NaHSO that mass fraction is 30% is slowly added dropwise3Aqueous solution generates light yellow crystal immediately, works as dropwise addition
NaHSO3When light yellow crystal no longer increases after aqueous solution, stop being added dropwise, reaction solution is filtered, obtains faint yellow solid crystalline substance
Body；Obtained solid crystal is washed twice through ethyl acetate mashing, 25 DEG C is put into, is dried in -0.95MPa drying boxes, do
Faint yellow solid product 167g is obtained after dry.
(4) solid product essence carries
Gained 167g solid products are added in three-necked flask, put up condensation reflux unit, and connect tail gas absorption.It is added
Then a certain amount of extractant ethyl acetate is added dropwise the acetic acid solution that mass fraction is 10%, opens stirring, and be heated to
70 DEG C of back flow reactions, solid product all dissolve and generate bulk gas discharge, until there is no bubble releasing in three-necked flask,
Stop reaction, system is made to be cooled to room temperature.By reaction solution stratification, organic layer is separated, is washed twice, the anhydrous sulphur of organic layer
Sour magnesium drying, revolving obtain citronellal crude oil 48g.
(5) citronellal crude oil purifies
48g citronellal crude oils are put into rectifying column, adjusting vacuum is 5MPa, adjusts the temperature to 30 DEG C, infinite reflux half is small
When.Light component is drawn clean；Slowly vacuum is adjusted until vacuum gives rectifying column to heat equal to 1MPa, with conduction oil, until rectifying
There is steam in tower mouth, is kept for infinite reflux state half an hour, then starts to discharge, and collects fraction and obtains methyl heptenone, methyl heptenyl
Temperature in tower is increased 5 DEG C with the rate of 2 DEG C/min when ketone will go out to the greatest extent；After waiting for that methyl heptenone has gone out, slowly adjust
Vacuum is saved to 0.1MPa, is heated up with the rate of 2 DEG C/min with conduction oil, until there is steam, is kept for infinite reflux state half an hour,
Then start to discharge, collect fraction and obtain citronellal, with the rate of 2 DEG C/min by temperature liter in tower when citronellal will go out to the greatest extent
It is 5 DEG C high；After waiting for that citronellal has gone out, is heated up with the rate of 2 DEG C/min with conduction oil, until there is steam, keep infinite reflux shape
Then state half an hour starts to discharge, collect fraction and obtain citral.Citronellal yield is 7g, and methyl heptenone yield is 11g, lemon
Lemon aldehyde yield about 1~2g.
Gas chromatographic analysis is carried out to gained citronellal product, analysis condition is：Shimadzu 2010plus gas chromatographs,
Db-5 low pole chromatographic columns, temperature programming are 80~250 DEG C, 10 DEG C of heating per minute.Known by gas chromatograph results, extraction obtains
Citronellal product in citronellal content be 98.19%.
Embodiment 3：
A kind of method that citronellal is extracted from fruit of a cubeb litsea tree hair oil of the present invention, wherein fruit of a cubeb litsea tree hair oil used is grey by mountain
Sub- fresh fruit warp slightly carries and distillation obtains, and specific extracting method is as follows：
(1) fruit of a cubeb litsea tree slightly carries：
The fruit of a cubeb litsea tree fresh fruit picked is cleaned up, weighs and fresh fruit 150kg is taken to be placed in water in alembic, mountain is added
The water (225kg) of grey 1.5 times of sub- fresh fruit weight.Using 4kg pressure vapor as heating carrier, and it is multi-functional using 1000L
Extraction element extracts, and adjusts the temperature and steam pressure of water distillation, and regurgitant volume is controlled in 150L/h；
After distillation, by the material in distillation through filter screen filtration, remaining water is then as feeding intake next time in flask
Use water.Upper layer dry fruit is discharged as byproduct, and Litsea Cubeba oil is released from oil water separator, amounts to 7.75kg.Water-oil separating
Water phase in device and the residual hydration of flask and total 192.3kg, into feeding intake next time.
(2) Litsea Cubeba oil distills
By in the Litsea Cubeba oil 2.0kg input 3L distilling flasks of preparation, the stirring of distilling flask is opened, vacuum is accessed.
Using heat-conducting oil heating；Vacuum pump is adjusted to 5MPa, and conduction oil temperature setting is 30 DEG C, and heating rate is 2 DEG C/min, starts to be discharged
Head；After head has gone out, distilling flask is heated up with 2 DEG C/min, until tower top temperature rises to 50 DEG C, keeps the mild heat conduction of flask
Oil temperature is constant, starts to discharge, and discharging substance is fruit of a cubeb litsea tree hair oil, amounts to discharging 396g.
(3) fruit of a cubeb litsea tree hair oil is refined
By in gained fruit of a cubeb litsea tree hair oil 396g input 1L three-necked flasks, magneton stirring is added, opens frozen cooling, waits for flask
When temperature drop is to 5 DEG C, the NaHSO that mass fraction is 20% is slowly added dropwise3Aqueous solution generates light yellow crystal immediately, works as dropwise addition
NaHSO3When light yellow crystal no longer increases after aqueous solution, stop being added dropwise, reaction solution is filtered, obtains faint yellow solid crystalline substance
Body；Obtained solid crystal is washed twice through ethyl acetate mashing, 25 DEG C is put into, is dried in -0.95MPa drying boxes, do
Faint yellow solid product 145g is obtained after dry.
(4) solid product essence carries
Gained 145g solid products are added in three-necked flask, put up condensation reflux unit, and connect tail gas absorption.It is added
Then a certain amount of extractant ethyl acetate is added dropwise the acetic acid solution that mass fraction is 10%, opens stirring, and be heated to
70 DEG C of back flow reactions, solid product all dissolve and generate bulk gas discharge, until there is no bubble releasing in three-necked flask,
Stop reaction, system is made to be cooled to room temperature.By reaction solution stratification, organic layer is separated, is washed twice, the anhydrous sulphur of organic layer
Sour magnesium drying, revolving obtain citronellal crude oil 41g.
(5) citronellal crude oil purifies
41 citronellal crude oils are put into rectifying column, adjusting vacuum is 5MPa, adjusts the temperature to 30 DEG C, infinite reflux half is small
When.Light component is drawn clean；Slowly vacuum is adjusted until vacuum gives rectifying column to heat equal to 1MPa, with conduction oil, until rectifying
There is steam in tower mouth, is kept for infinite reflux state half an hour, then starts to discharge, and collects fraction and obtains methyl heptenone, methyl heptenyl
Temperature in tower is increased 5 DEG C with the rate of 2 DEG C/min when ketone will go out to the greatest extent；After waiting for that methyl heptenone has gone out, slowly adjust
Vacuum is saved to 0.1MPa, is heated up with the rate of 2 DEG C/min with conduction oil, until there is steam, is kept for infinite reflux state half an hour,
Then start to discharge, collect fraction and obtain citronellal, with the rate of 2 DEG C/min by temperature liter in tower when citronellal will go out to the greatest extent
It is 5 DEG C high；After waiting for that citronellal has gone out, is heated up with the rate of 2 DEG C/min with conduction oil, until there is steam, keep infinite reflux shape
Then state half an hour starts to discharge, collect fraction and obtain citral.Citronellal yield is 10g, and methyl heptenone yield is 12g, lemon
Lemon aldehyde yield about 1~2g.
Gas chromatographic analysis is carried out to gained citronellal product, analysis condition is：Shimadzu 2010plus gas chromatographs,
Db-5 low pole chromatographic columns, temperature programming are 80~250 DEG C, 10 DEG C of heating per minute.Known by gas chromatograph results, extraction obtains
Citronellal product in citronellal content be 98.29%.
Claims (10)
1. a kind of method for extracting citronellal in hair oil from the fruit of a cubeb litsea tree, which is characterized in that include the following steps：
(1) fruit of a cubeb litsea tree hair oil is put into reaction vessel, control temperature of reaction system is 5~15 DEG C, and NaHSO is added dropwise3Aqueous solution with
Addition reaction occurs for aldehyde, ketone in fruit of a cubeb litsea tree hair oil, obtains the solid product insoluble in fruit of a cubeb litsea tree hair oil；
(2) step (1) obtained solid product is detached, extractant is added, acid solution is then added dropwise, 68~72 are warming up under stirring
DEG C back flow reaction, stratification after reaction, organic layer is washed, it is dry after, obtain citronellal crude oil；
(3) by citronellal crude oil input rectifying column obtained by step (2), point three sections of progress rectifying obtain methyl heptenone, perfume (or spice) respectively
Thatch aldehyde and citral.
2. the method for extracting citronellal in the hair oil according to claim 1 from the fruit of a cubeb litsea tree, which is characterized in that the step
(3) in, point three sections of progress rectifying specifically refer to, first segment rectifying：Vacuum degree is 0.9~1.1MPa in control tower, temperature in tower
It is 45~55 DEG C, collects fraction and obtain methyl heptenone；Second segment rectifying：Vacuum degree is 0.09~0.11MPa in control tower, in tower
Temperature is 45~55 DEG C, collects fraction and obtains citronellal；Third section rectifying：Vacuum degree is 0.09~0.11MPa in control tower, in tower
Temperature is 70~74 DEG C, collects fraction and obtains citral.
3. the method for extracting citronellal in the hair oil according to claim 2 from the fruit of a cubeb litsea tree, which is characterized in that the step
(3) in, before carrying out first segment rectifying, vacuum degree is 4~6MPa in first adjusting tower, and temperature is 25~35 DEG C in tower, makes tower
25~35min of interior citronellal crude oil boiling, the light component in citronellal crude oil is steamed.
4. the method for extracting citronellal in the hair oil according to claim 2 from the fruit of a cubeb litsea tree, which is characterized in that the step
(3) in, first segment rectifying the specific steps are：
Vacuum degree is 0.9~1.1MPa in slow adjusting tower, is added rectifying column with the rate of 1.8~2.2 DEG C/min with conduction oil
Heat makes rectifying column mouth steam occur to 45~55 DEG C, then keeps 25~35min of infinite reflux, starts to discharge, collect this section of fraction
Methyl heptenone is obtained, temperature in tower is increased 4~6 with the rate of 1.8~2.2 DEG C/min when methyl heptenone will go out to the greatest extent
℃。
5. the method for extracting citronellal in the hair oil according to claim 2 from the fruit of a cubeb litsea tree, which is characterized in that the step
(3) in, second segment rectifying the specific steps are：
After waiting for that methyl heptenone has gone out, vacuum degree is to 0.09~0.11MPa in slow adjusting tower, with conduction oil with 1.8~2.2
DEG C/rectifying column is warming up to 45~55 DEG C by the rate of min, and rectifying column mouth is made steam occur, then keep infinite reflux 25~
35min starts to discharge, and collects this section of fraction and obtains citronellal, with the speed of 1.8~2.2 DEG C/min when citronellal will go out to the greatest extent
Temperature in tower is increased 4~6 DEG C by rate.
6. the method for extracting citronellal in the hair oil according to claim 2 from the fruit of a cubeb litsea tree, which is characterized in that the step
(3) in, third section rectifying the specific steps are：
After waiting for that citronellal has gone out, rectifying column is warming up to 70~74 DEG C with the rate of 1.8~2.2 DEG C/min with conduction oil, is made
There is steam in rectifying column mouth, then keeps 25~35min of infinite reflux, starts to discharge, collect this section of fraction and obtain citral, citral
Temperature in tower is increased 4~6 DEG C with the rate of 1.8~2.2 DEG C/min when will going out to the greatest extent.
7. the method for extracting citronellal in the hair oil according to claim 1 from the fruit of a cubeb litsea tree, which is characterized in that the fruit of a cubeb litsea tree
Hair oil is prepared via a method which to obtain：
Fruit of a cubeb litsea tree fresh fruit is washed, is placed in alembic, the water of 1.5~2 times of fruit of a cubeb litsea tree weight is added, is carried using volatile oil
It takes device to extract, obtains Litsea Cubeba oil；Gained Litsea Cubeba oil is added in distilling flask, vacuumizes and is distilled, is controlled
Vacuum degree is 0.09~0.11MPa, and distilling flask top temperature is 45~55 DEG C, collects fraction to get fruit of a cubeb litsea tree hair oil.
8. the method for extracting citronellal in the hair oil according to claim 7 from the fruit of a cubeb litsea tree, which is characterized in that the alembic
Using 6~8kg pressure vapor as heating carrier；Regurgitant volume in alembic is controlled in 125~175L/h.
9. the method for extracting citronellal in the hair oil according to claim 1 from the fruit of a cubeb litsea tree, which is characterized in that the step
(2) in, extractant is nonpolar or low pole extractant, any one in ethyl acetate, petroleum ether, ether, hexamethylene
Kind.
10. according to the method for extracting citronellal in the hair oil according to any one of claims 1 to 9 from the fruit of a cubeb litsea tree, feature exists
In in the step (2), the drier used in drying process is neutral or faintly acid drier, is selected from anhydrous magnesium sulfate or nothing
Water calcium chloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342099A (en) * | 2019-08-09 | 2021-02-09 | 南风化工集团股份有限公司 | Production method of plant bacteriostatic mosquito-repellent essential oil soap |
| CN113816840A (en) * | 2021-10-21 | 2021-12-21 | 昆山亚香香料股份有限公司 | Synthesis method of beta-damascenone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237323A (en) * | 2015-10-20 | 2016-01-13 | 永州山香香料有限公司 | Method for extracting limonene from litsea cubeba |
| CN106350230A (en) * | 2016-12-05 | 2017-01-25 | 永州山香香料有限公司 | Litsea cubeba oil distillation separation equipment and technology |
-
2017
- 2017-12-15 CN CN201711350165.1A patent/CN108383702B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237323A (en) * | 2015-10-20 | 2016-01-13 | 永州山香香料有限公司 | Method for extracting limonene from litsea cubeba |
| CN106350230A (en) * | 2016-12-05 | 2017-01-25 | 永州山香香料有限公司 | Litsea cubeba oil distillation separation equipment and technology |
Non-Patent Citations (4)
| Title |
|---|
| DANIEL CHONG JUN WENG等: "Separation of Geraniol from Citronellol by Selective Oxidation of Geraniol to Geranial", 《SAINS MALAYSIANA》 * |
| DEWI HAFIDLOH等: "The effect of base catalyst in the citronellal purification of kaffir lime oil precipitated by NaHSO3 and Na2SO3", 《BULETIN PENELITIAN TANAMAN REMPAH DAN OBAT》 * |
| 叶锦标等: "山鸡椒根中香茅醛的分离鉴定", 《中药材》 * |
| 陈民桥等: "香茅油化学单离法的研究", 《海南大学学报自然科学版》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342099A (en) * | 2019-08-09 | 2021-02-09 | 南风化工集团股份有限公司 | Production method of plant bacteriostatic mosquito-repellent essential oil soap |
| CN113816840A (en) * | 2021-10-21 | 2021-12-21 | 昆山亚香香料股份有限公司 | Synthesis method of beta-damascenone |
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