CN108383702B - Method for extracting citronellal from litsea cubeba head oil - Google Patents
Method for extracting citronellal from litsea cubeba head oil Download PDFInfo
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Abstract
The invention discloses a method for extracting citronellal from litsea cubeba head oil, which comprises the following steps: (1) adding litsea cubeba oil into a reaction container, controlling the temperature of a reaction system to be 5-15 ℃, and dropwise adding NaHSO3Performing addition reaction on the aqueous solution and aldehyde ketone in the litsea cubeba head oil to obtain a solid product insoluble in the litsea cubeba head oil; (2) separating the solid product obtained in the step (1), adding an extracting agent, then dropwise adding an acid solution, heating to 68-72 ℃ under stirring for reflux reaction, standing for layering after the reaction is finished, and washing and drying an organic layer to obtain crude citronellal oil; (3) and (3) putting the citronellal crude oil obtained in the step (2) into a rectifying tower, and rectifying in three sections to respectively obtain methyl heptenone, citronellal and citral. The method has the advantages of convenient operation, low cost, high efficiency and high product purity, and can be used for coproducing methyl heptenone and citral.
Description
Technical Field
The invention relates to the technical field of citronellal extraction, and particularly relates to a method for extracting citronellal from litsea cubeba oil.
Background
Citronellal is an important isolated perfume with a strong, fresh, green-orange-like, slightly woody aroma. Citronellal is widely used in edible essences, for preparing citrus and cherry essences, as an essence for preparing low-grade soap, as a raw material of other spices, and for synthesizing hydroxycitronellal, menthol and other spices. The citronellal is derived from two kinds of natural extraction and chemical synthesis. Because the synthesized citronellal carries more uncertain impurities, the citronellal is used as the edible essence and has unpredictable harm to human bodies.
Litsea cubeba oil, which contains citronellal and contains no substances with specific harm to human body as chemical components, has been used as a food additive for more than 30 years. In addition, there is an increasing demand for natural citral, resulting in more and more litsea cubeba oil (a front fraction of litsea cubeba oil) being wasted as a by-product.
Disclosure of Invention
In view of the above-mentioned shortcomings and drawbacks of the prior art, the present invention aims to provide a method for extracting citronellal from pungent litse fruit oil, which is convenient to operate, high in efficiency, high in product purity, and capable of co-producing methylheptenone and citral.
A method for extracting citronellal from litsea cubeba oil comprises the following steps:
(1) adding litsea cubeba oil into a reaction container, controlling the temperature of a reaction system to be 5-15 ℃, and dropwise adding NaHSO3Performing addition reaction on the aqueous solution and aldehyde ketone in the litsea cubeba head oil to obtain a solid product insoluble in the litsea cubeba head oil;
(2) separating the solid product obtained in the step (1), adding an extracting agent, then dropwise adding an acid solution, heating to 68-72 ℃ under stirring for reflux reaction, standing for layering after the reaction is finished, and washing and drying an organic layer to obtain crude citronellal oil;
(3) and (3) putting the citronellal crude oil obtained in the step (2) into a rectifying tower, rectifying in three sections, and rectifying in three sections to respectively obtain methyl heptenone, citronellal and citral.
The invention adds NaHSO into litsea cubeba oil3Aqueous solution, controlling the temperature of a reaction system to be 5-15 ℃, and passing through NaHSO3Performing characteristic addition reaction with aldehyde ketone in the litsea cubeba head oil to generate a solid intermediate product, separating the solid intermediate product, dripping an acid solution, stirring, performing reflux reaction to remove sulfonic groups from the intermediate product, returning the intermediate product to the aldehyde ketone, and separating citronellal and other aldehyde and ketone substances from the litsea cubeba head oil to obtain crude citronellal oil; then, the citronellal and the methylheptyl are separated from the crude citronellal oil by rectification and controlling the vacuum degree and the temperature in the towerKetene and citral. The method has the advantages of convenient operation, low cost, high efficiency and high product purity, and can be used for coproducing methyl heptenone and citral. In the step (1), aldehyde ketone and NaHSO in litsea cubeba oil3In the reaction process, the reaction temperature needs to be controlled at 5-15 ℃, side reactions are increased if the reaction temperature is too high, and the yield of the citronellal is greatly reduced.
In a preferred scheme, in the step (3), the rectification in three sections specifically means that the rectification in the first section is as follows: controlling the vacuum degree in the tower to be 0.9-1.1 MPa, controlling the temperature in the tower to be 45-55 ℃, and collecting fractions to obtain methyl heptenone; second-stage rectification: controlling the vacuum degree in the tower to be 0.09-0.11 MPa, controlling the temperature in the tower to be 45-55 ℃, and collecting fractions to obtain citronellal; and (3) third-stage rectification: controlling the vacuum degree in the tower to be 0.09-0.11 MPa, controlling the temperature in the tower to be 70-74 ℃, and collecting the fraction to obtain the citral. By controlling the vacuum degree and the temperature in the rectifying tower within the range, the methyl heptenone, the citronellal and the citral are collected in sections, and the obtained product has high purity.
In a preferred scheme, in the step (3), the first-stage rectification comprises the following specific steps: slowly adjusting the vacuum degree in the tower to be 0.9-1.1 MPa, heating the rectifying tower to 45-55 ℃ by using heat conduction oil at the speed of 1.8-2.2 ℃/min to enable steam to appear at the mouth of the rectifying tower, then maintaining total reflux for 25-35 min, starting discharging, collecting the fraction to obtain methyl heptenone, and raising the temperature in the tower by 4-6 ℃ at the speed of 1.8-2.2 ℃/min when the methyl heptenone is about to be exhausted.
In a further preferred scheme, in the step (3), the first-stage rectification specifically comprises the following steps: slowly adjusting the vacuum degree in the tower to 1MPa, heating the rectifying tower to 50 ℃ at the speed of 2 ℃/min by using heat conduction oil, enabling steam to appear at the mouth of the rectifying tower, then keeping total reflux for 30min, starting discharging, collecting the fraction to obtain methyl heptenone, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the methyl heptenone is about to be exhausted.
In a preferred scheme, in the step (3), the second stage of rectification comprises the following specific steps: after the methyl heptenone is discharged, slowly adjusting the vacuum degree in the rectifying tower to 0.09-0.11 MPa, heating the rectifying tower to 45-55 ℃ at the speed of 1.8-2.2 ℃/min by using heat conducting oil, enabling steam to appear at the mouth of the rectifying tower, then maintaining total reflux for 25-35 min, starting discharging, collecting fractions at the section to obtain citronellal, and raising the temperature in the rectifying tower to 4-6 ℃ at the speed of 1.8-2.2 ℃/min when the citronellal is about to be discharged completely.
In a further preferred scheme, in the step (3), the specific steps of the second-stage rectification are as follows: after finishing the discharge of the methylheptenone, slowly adjusting the vacuum degree in the tower to 0.1MPa, heating the rectifying tower to 50 ℃ at the speed of 2 ℃/min by using heat conduction oil, leading steam to appear at the mouth of the rectifying tower, then keeping the total reflux for 30min, starting discharging, collecting the fraction to obtain citronellal, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the citronellal is about to be discharged.
In a preferred scheme, in the step (3), the third stage of rectification comprises the following specific steps: after the citronellal is completely discharged, heating the rectifying tower to 70-74 ℃ by using heat conduction oil at the speed of 1.8-2.2 ℃/min, enabling steam to appear at the mouth of the rectifying tower, then maintaining total reflux for 25-35 min, starting discharging, collecting fractions at the section to obtain citral, and when the citral is about to be discharged, heating the temperature in the rectifying tower to 4-6 ℃ at the speed of 1.8-2.2 ℃/min.
In a further preferred scheme, in the step (3), the third stage of rectification specifically comprises the following steps: after the citronellal is completely discharged, heating the rectifying tower to 72 ℃ at the speed of 2 ℃/min by using heat conduction oil, enabling steam to appear at the mouth of the rectifying tower, then keeping the total reflux for 30min, starting discharging, collecting the fraction to obtain citral, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the citral is about to be discharged.
In a further preferable scheme, in the step (3), the vacuum degree in the tower is controlled to be 1MPa in the first-stage rectification and the second-stage rectification, the temperature in the tower is controlled to be 50 ℃, the vacuum degree in the tower is controlled to be 0.1MPa in the third-stage rectification, and the temperature in the tower is controlled to be 72 ℃.
In the preferable scheme, in the step (3), before the first-stage rectification, the vacuum degree in the tower is adjusted to be 4-6 MPa, the temperature in the tower is 25-35 ℃, the citronellal crude oil in the tower is boiled for 25-35 min, and light components in the citronellal crude oil are evaporated.
In a further preferable scheme, in the step (3), before the first-stage rectification, the vacuum degree in the tower is adjusted to be 5MPa, the temperature in the tower is 30 ℃, the crude citronellal oil in the tower is boiled for 30min, and light components in the crude citronellal oil are evaporated.
Before the first-stage rectification, the light components in the citronellal crude oil are evaporated by adjusting the vacuum degree and the temperature in the tower, so that the light components are prevented from being mixed into the rectification product, and the purity of the methyl heptenone, citronellal and citral products is improved.
Preferably, in step (1), NaHSO3Dripping the aqueous solution into litsea cubeba oil to generate light yellow crystals, and dripping NaHSO3Stopping dripping when the light yellow crystals are not increased any more after the water solution, filtering the reaction solution, and washing and drying filter residues to obtain a solid product.
In a further preferred embodiment, in step (1), the solvent used in the washing operation is a non-polar or weakly polar organic solvent, and the non-polar or weakly polar organic solvent is selected from any one of ethyl acetate, petroleum ether, diethyl ether and cyclohexane, and is further preferably diethyl ether.
Preferably, in step (2), the extractant is selected from any one of ethyl acetate, petroleum ether, diethyl ether and cyclohexane, and diethyl ether is more preferred.
Preferably, in the step (2), the acid solution is 10% by mass of acetic acid solution, and the reflux temperature is 70 ℃.
Preferably, in the step (1), the temperature of the reaction system is controlled at 10 ℃ and NaHSO3The mass fraction of the aqueous solution was 25%.
Preferably, in the step (2), the drying agent used in the drying operation is a neutral or weakly acidic drying agent selected from anhydrous magnesium sulfate or anhydrous calcium chloride, and more preferably anhydrous magnesium sulfate.
The litsea cubeba head oil used in the invention can be a byproduct (stored litsea cubeba head oil) obtained by the existing citral extraction process, and can also be prepared from fresh litsea cubeba fruits by the following method:
washing the fresh litsea cubeba fruits, placing the washed fresh litsea cubeba fruits in a distillation retort, adding residual water (obtained after the last distillation and filtration of materials, and supplementing part of the lost water with clear water) in a flask, wherein the weight of the residual water is 1.5-2 times (more preferably 1.5 times) that of the litsea cubeba fruits, and extracting the residual water by using a volatile oil extractor to obtain crude oil of the litsea cubeba;
adding the obtained crude oil of the litsea cubeba into a distillation flask, vacuumizing and distilling, controlling the vacuum degree to be 0.09-0.11 MPa and the top temperature of the distillation flask to be 45-55 ℃, and collecting fractions to obtain the litsea cubeba oil.
In a further preferable scheme, the vacuum degree is controlled to be 0.1MPa when the litsea cubeba crude oil is distilled in vacuum, and the top temperature of a distillation flask is controlled to be 50 ℃.
In a further preferable scheme, 4-8 kg of pressure steam is used as a heating carrier in the distillation tank; the reflux amount in the distillation tank is controlled to be 125-175L/h. The pressure of the steam is more preferably 6kg, and the amount of reflux is more preferably 150L/h.
Compared with the prior art, the invention has the advantages that: the invention firstly mixes aldehyde ketone in litsea cubeba head oil with NaHSO3Performing addition reaction to generate a solid intermediate product insoluble in the oil phase; then, the solid intermediate product is subjected to reverse reaction through an acid solution and returns to aldehyde ketone, so that substances in the aldehyde ketone are separated from the litsea cubeba oil, and crude citronellal oil is obtained; and then the citronellal crude oil is rectified in sections to obtain methyl heptenone, citronellal and citral. The preparation method has the advantages of simple preparation process, low cost and high production efficiency, the purity of the obtained citronellal is up to more than 98%, and byproducts methyl heptenone and citral with high added values can be co-produced. The raw material of the invention can be the litsea cubeba head oil obtained by crude extraction and distillation of fresh litsea cubeba fruits, and can also be a litsea cubeba head oil byproduct obtained in the production process of citral, thereby solving the problems of waste and inventory of the litsea cubeba head oil in the prior citral production.
Drawings
FIG. 1 is a gas chromatography analysis chart of citronellal obtained in example 1 of the present invention.
FIG. 2 is the gas chromatographic data of citronellal in FIG. 1.
FIG. 3 is a photograph of a sample of citronellal obtained in example 1 of the present invention.
FIG. 4 is a gas chromatography analysis chart of methylheptenone obtained in example 1 of the present invention.
Fig. 5 is gas chromatographic data for methylheptenone of fig. 4.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a method for extracting citronellal from litsea cubeba head oil, wherein the litsea cubeba head oil is obtained by crude extraction and distillation of fresh litsea cubeba fruits, and the specific extraction method comprises the following steps:
(1) crude extraction of litsea cubeba:
the picked fresh litsea cubeba fruits are cleaned, 150kg of the fresh litsea cubeba fruits are weighed and placed in a water distillation retort, and water (225kg) with the weight 1.5 times of that of the fresh litsea cubeba fruits is added. Adopting 4kg pressure steam as heating carrier, extracting with 1000L multifunctional extraction device, adjusting distillation temperature and steam pressure in water, and controlling reflux amount at 150L/h;
after distillation, the materials in the distillation flask are filtered by a filter screen, and the residual water in the flask is used as the water for next feeding. The upper layer of dried fruits are discharged as a byproduct, and crude litsea cubeba oil is discharged from the oil-water separator, and the total amount is 7.75 kg. The water phase in the oil-water separator and the residual water in the flask were combined to give 192.3kg in total, and the next charge was made.
(2) Distilling crude oil of litsea cubeba
2.0kg of the prepared litsea cubeba crude oil is put into a 3L distillation flask, the stirring of the distillation flask is started, and the vacuum is switched on. Heating by adopting heat conducting oil; adjusting the vacuum pump to 5MPa, setting the temperature of the heat-conducting oil to 30 ℃, and starting a water outlet head when the temperature rise rate is 2 ℃/min; after the water head is discharged, heating the distillation flask at 2 ℃/min until the temperature at the top of the tower rises to 50 ℃, keeping the temperature of the flask and the heat conducting oil unchanged, and starting discharging, wherein the discharged material is litsea cubeba oil, and the total amount of discharged materials is 392 g.
(3) Refining litsea cubeba head oil
Putting 392g of the obtained litsea cubeba oil into a 1L three-neck flask, adding magnetons, stirring, starting freezing and cooling, and slowly dropwise adding NaHSO with the mass fraction of 25% when the temperature of the flask is reduced to 10 DEG C3The aqueous solution immediately produces pale yellow crystals, and NaHSO is added dropwise3Stopping dripping when the amount of the light yellow crystals is not increased after the water solution is added, and performing suction filtration on the reaction solution to obtain light yellow solid crystals; pulping and washing the obtained solid crystal twice by ethyl acetate, drying in a drying oven at 25 ℃ and-0.95 MPa to obtain 154g of light yellow solid product.
(4) Fine extraction of solid product
154g of the obtained solid product is added into a three-neck flask, a condensation reflux device is built, and tail gas absorption is carried out. Adding a certain amount of extractant ethyl acetate, then dropwise adding 10% by mass of acetic acid solution, starting stirring, heating to 70 ℃ for reflux reaction, completely dissolving solid products, generating a large amount of gas to be discharged until no more bubbles are discharged from the three-neck flask, stopping reaction, and cooling the system to normal temperature. And standing the reaction solution for layering, separating an organic layer, washing with water twice, drying the organic layer with anhydrous magnesium sulfate, and performing rotary evaporation to obtain 43g of citronellal crude oil.
(5) Purification of crude citronellal oil
Putting 43g of citronellal crude oil into a rectifying tower, adjusting the vacuum to 5MPa, adjusting the temperature to 30 ℃, and carrying out total reflux for half an hour. Cleaning the light component; slowly adjusting vacuum until the vacuum is equal to 1MPa, heating the rectifying tower by using heat conduction oil until steam appears at the opening of the rectifying tower, keeping a full reflux state for half an hour, then starting discharging, collecting fractions to obtain methyl heptenone, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the methyl heptenone is about to be exhausted; after finishing the discharge of the methylheptenone, slowly adjusting the vacuum to 0.1MPa, heating with heat conduction oil at the speed of 2 ℃/min until steam appears, keeping the total reflux state for half an hour, then starting discharging, collecting fractions to obtain citronellal, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the citronellal is about to be discharged; after the citronellal is discharged, heating up by using heat conduction oil at the speed of 2 ℃/min until steam appears, keeping the total reflux state for half an hour, then discharging, and collecting the fraction to obtain the citral. The yield of citronellal is 11g, the yield of methylheptenone is 15g, and the yield of citral is about 1-2 g.
Performing gas chromatography analysis on the obtained citronellal product, wherein the analysis conditions are as follows: the temperature programming of the Shimadzu 2010plus gas chromatograph and the Db-5 weak polarity chromatographic column is 80-250 ℃ and 10 ℃ per minute.
The chromatogram analysis chart of the citronellal product is shown in FIG. 1, FIG. 2 is the gas chromatogram data chart in FIG. 1, and it can be seen from FIGS. 1 and 2 that the content of citronellal in the extracted citronellal product is 98.37% (corresponding to retention time 7.449). A photograph of a sample of the resulting citronellal product is shown in FIG. 3.
And (3) carrying out gas chromatography analysis on the obtained methylheptenone under the analysis conditions: the temperature rise method of the gas chromatograph of the Shimadzu 2010plus and the Db-5 weak polarity chromatographic column is that the temperature rise is 2 ℃ per minute at the temperature range of 80-140 ℃ and 10 ℃ per minute at the temperature range of 140-250 ℃.
The chromatogram analysis chart of the obtained methylheptenone is shown in FIG. 4, the gas chromatogram data is shown in FIG. 5, and as can be seen from FIGS. 4 and 5, the content of methylheptenone in the extracted methylheptenone product is 99.19% (corresponding to retention time of 13.779)
Example 2:
the invention relates to a method for extracting citronellal from litsea cubeba head oil, wherein the litsea cubeba head oil is obtained by crude extraction and distillation of fresh litsea cubeba fruits, and the specific extraction method comprises the following steps:
(1) crude extraction of litsea cubeba:
the picked fresh litsea cubeba fruits are cleaned, 150kg of the fresh litsea cubeba fruits are weighed and placed in a water distillation retort, and water (225kg) with the weight 1.5 times of that of the fresh litsea cubeba fruits is added. Adopting 4kg pressure steam as heating carrier, extracting with 1000L multifunctional extraction device, adjusting distillation temperature and steam pressure in water, and controlling reflux amount at 150L/h;
after distillation is finished, filtering materials in distillation through a filter screen, and taking residual water in the flask as water for next feeding. The upper layer of dried fruits are discharged as a byproduct, and crude litsea cubeba oil is discharged from the oil-water separator, and the total amount is 7.75 kg. The water phase in the oil-water separator and the residual water in the flask were combined to give 192.3kg in total, and the next charge was made.
(2) Distilling crude oil of litsea cubeba
2.0kg of the prepared litsea cubeba crude oil is put into a 3L distillation flask, the stirring of the distillation flask is started, and the vacuum is switched on. Heating by adopting heat conducting oil; adjusting the vacuum pump to 5MPa, setting the temperature of the heat-conducting oil to 30 ℃, and starting a water outlet head when the temperature rise rate is 2 ℃/min; after the water head is discharged, heating the distillation flask at 2 ℃/min until the temperature at the top of the tower rises to 50 ℃, keeping the temperature of the flask and the heat conducting oil unchanged, starting discharging, wherein the discharged material is litsea cubeba oil, and the total amount of discharged materials is 403 g.
(3) Refining litsea cubeba head oil
Putting 403g of the obtained litsea cubeba oil into a 1L three-neck flask, adding magnetons, stirring, starting freezing and cooling, and slowly dropwise adding NaHSO with the mass fraction of 30% when the temperature of the flask is reduced to 15 DEG C3The aqueous solution immediately produces pale yellow crystals, and NaHSO is added dropwise3Stopping dripping when the amount of the light yellow crystals is not increased after the water solution is added, and performing suction filtration on the reaction solution to obtain light yellow solid crystals; pulping and washing the obtained solid crystal twice by ethyl acetate, drying in a drying box at 25 ℃ and-0.95 MPa to obtain 167g of light yellow solid product.
(4) Fine extraction of solid product
167g of the obtained solid product is added into a three-neck flask, a condensation reflux device is built, and tail gas absorption is carried out. Adding a certain amount of extractant ethyl acetate, then dropwise adding 10% by mass of acetic acid solution, starting stirring, heating to 70 ℃ for reflux reaction, completely dissolving solid products, generating a large amount of gas to be discharged until no more bubbles are discharged from the three-neck flask, stopping reaction, and cooling the system to normal temperature. And standing the reaction solution for layering, separating an organic layer, washing with water twice, drying the organic layer with anhydrous magnesium sulfate, and performing rotary evaporation to obtain 48g of crude citronellal oil.
(5) Purification of crude citronellal oil
Putting 48g of citronellal crude oil into a rectifying tower, adjusting the vacuum to 5MPa, adjusting the temperature to 30 ℃, and carrying out total reflux for half an hour. Cleaning the light component; slowly adjusting vacuum until the vacuum is equal to 1MPa, heating the rectifying tower by using heat conduction oil until steam appears at the opening of the rectifying tower, keeping a full reflux state for half an hour, then starting discharging, collecting fractions to obtain methyl heptenone, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the methyl heptenone is about to be exhausted; after finishing the discharge of the methylheptenone, slowly adjusting the vacuum to 0.1MPa, heating with heat conduction oil at the speed of 2 ℃/min until steam appears, keeping the total reflux state for half an hour, then starting discharging, collecting fractions to obtain citronellal, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the citronellal is about to be discharged; after the citronellal is discharged, heating up by using heat conduction oil at the speed of 2 ℃/min until steam appears, keeping the total reflux state for half an hour, then discharging, and collecting the fraction to obtain the citral. The yield of citronellal is 7g, the yield of methylheptenone is 11g, and the yield of citral is about 1-2 g.
Performing gas chromatography analysis on the obtained citronellal product, wherein the analysis conditions are as follows: the temperature programming of the Shimadzu 2010plus gas chromatograph and the Db-5 weak polarity chromatographic column is 80-250 ℃ and 10 ℃ per minute. The content of citronellal in the extracted citronellal product is 98.19% as shown by gas chromatography.
Example 3:
the invention relates to a method for extracting citronellal from litsea cubeba head oil, wherein the litsea cubeba head oil is obtained by crude extraction and distillation of fresh litsea cubeba fruits, and the specific extraction method comprises the following steps:
(1) crude extraction of litsea cubeba:
the picked fresh litsea cubeba fruits are cleaned, 150kg of the fresh litsea cubeba fruits are weighed and placed in a water distillation retort, and water (225kg) with the weight 1.5 times of that of the fresh litsea cubeba fruits is added. Adopting 4kg pressure steam as heating carrier, extracting with 1000L multifunctional extraction device, adjusting distillation temperature and steam pressure in water, and controlling reflux amount at 150L/h;
after distillation is finished, filtering materials in distillation through a filter screen, and taking residual water in the flask as water for next feeding. The upper layer of dried fruits are discharged as a byproduct, and crude litsea cubeba oil is discharged from the oil-water separator, and the total amount is 7.75 kg. The water phase in the oil-water separator and the residual water in the flask were combined to give 192.3kg in total, and the next charge was made.
(2) Distilling crude oil of litsea cubeba
2.0kg of the prepared litsea cubeba crude oil is put into a 3L distillation flask, the stirring of the distillation flask is started, and the vacuum is switched on. Heating by adopting heat conducting oil; adjusting the vacuum pump to 5MPa, setting the temperature of the heat-conducting oil to 30 ℃, and starting a water outlet head when the temperature rise rate is 2 ℃/min; after the water head is discharged, heating the distillation flask at 2 ℃/min until the temperature at the top of the tower is raised to 50 ℃, keeping the temperature of the mild heat conducting oil in the flask unchanged, starting discharging, wherein the discharged material is litsea cubeba oil, and the total amount of discharged material is 396 g.
(3) Refining litsea cubeba head oil
Putting 396g of the obtained litsea cubeba oil into a 1L three-neck flask, adding magnetons, stirring, starting freezing and cooling, and slowly dropwise adding NaHSO with the mass fraction of 20% when the temperature of the flask is reduced to 5 DEG C3The aqueous solution immediately produces pale yellow crystals, and NaHSO is added dropwise3Stopping dripping when the amount of the light yellow crystals is not increased after the water solution is added, and performing suction filtration on the reaction solution to obtain light yellow solid crystals; pulping and washing the obtained solid crystal twice by ethyl acetate, drying in a drying oven at 25 ℃ and-0.95 MPa to obtain 145g of light yellow solid product.
(4) Fine extraction of solid product
145g of the obtained solid product is added into a three-neck flask, a condensation reflux device is built, and tail gas absorption is carried out. Adding a certain amount of extractant ethyl acetate, then dropwise adding 10% by mass of acetic acid solution, starting stirring, heating to 70 ℃ for reflux reaction, completely dissolving solid products, generating a large amount of gas to be discharged until no more bubbles are discharged from the three-neck flask, stopping reaction, and cooling the system to normal temperature. And standing the reaction solution for layering, separating an organic layer, washing with water twice, drying the organic layer with anhydrous magnesium sulfate, and performing rotary evaporation to obtain 41g of crude citronellal oil.
(5) Purification of crude citronellal oil
Putting the 41 citronellal crude oil into a rectifying tower, adjusting the vacuum to 5MPa, adjusting the temperature to 30 ℃, and performing total reflux for half an hour. Cleaning the light component; slowly adjusting vacuum until the vacuum is equal to 1MPa, heating the rectifying tower by using heat conduction oil until steam appears at the opening of the rectifying tower, keeping a full reflux state for half an hour, then starting discharging, collecting fractions to obtain methyl heptenone, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the methyl heptenone is about to be exhausted; after finishing the discharge of the methylheptenone, slowly adjusting the vacuum to 0.1MPa, heating with heat conduction oil at the speed of 2 ℃/min until steam appears, keeping the total reflux state for half an hour, then starting discharging, collecting fractions to obtain citronellal, and raising the temperature in the tower by 5 ℃ at the speed of 2 ℃/min when the citronellal is about to be discharged; after the citronellal is discharged, heating up by using heat conduction oil at the speed of 2 ℃/min until steam appears, keeping the total reflux state for half an hour, then discharging, and collecting the fraction to obtain the citral. The yield of citronellal is 10g, the yield of methylheptenone is 12g, and the yield of citral is about 1-2 g.
Performing gas chromatography analysis on the obtained citronellal product, wherein the analysis conditions are as follows: the temperature programming of the Shimadzu 2010plus gas chromatograph and the Db-5 weak polarity chromatographic column is 80-250 ℃ and 10 ℃ per minute. The content of citronellal in the extracted citronellal product is 98.29% as shown by the result of gas chromatography.
Claims (9)
1. A method for extracting citronellal from litsea cubeba oil is characterized by comprising the following steps: (1) adding litsea cubeba oil into a reaction container, controlling the temperature of a reaction system to be 5-15 ℃, and dropwise adding NaHSO3Performing addition reaction on the aqueous solution and aldehyde and ketone in the litsea cubeba head oil to obtain a solid product insoluble in the litsea cubeba head oil; (2) separating the solid product obtained in the step (1), adding an extracting agent ethyl acetate, then dropwise adding an acetic acid solution, and stirringHeating to 68-72 ℃ for reflux reaction, standing for layering after the reaction is finished, and washing and drying an organic layer to obtain crude citronellal oil; (3) and (3) putting the citronellal crude oil obtained in the step (2) into a rectifying tower, and rectifying in three sections to respectively obtain methyl heptenone, citronellal and citral.
2. The method for extracting citronellal from litsea cubeba oil as claimed in claim 1, wherein in the step (3), the rectification in three stages is specifically a first stage rectification: controlling the vacuum degree in the tower to be 0.9-1.1 MPa, controlling the temperature in the tower to be 45-55 ℃, and collecting fractions to obtain methyl heptenone; second-stage rectification: controlling the vacuum degree in the tower to be 0.09-0.11 MPa, controlling the temperature in the tower to be 45-55 ℃, and collecting fractions to obtain citronellal; and (3) third-stage rectification: controlling the vacuum degree in the tower to be 0.09-0.11 MPa, controlling the temperature in the tower to be 70-74 ℃, and collecting the fraction to obtain the citral.
3. The method for extracting citronellal from litsea cubeba oil as claimed in claim 2, wherein in step (3), before the first-stage rectification, the vacuum degree in the tower is adjusted to 4-6 MPa, the temperature in the tower is adjusted to 25-35 ℃, the crude citronellal oil in the tower is boiled for 25-35 min, and light components in the crude citronellal oil are distilled out.
4. The method for extracting citronellal from litsea cubeba oil as claimed in claim 2, wherein in the step (3), the first stage of rectification comprises the following specific steps: slowly adjusting the vacuum degree in the tower to be 0.9-1.1 MPa, heating the rectifying tower to 45-55 ℃ by using heat conduction oil at the speed of 1.8-2.2 ℃/min to enable steam to appear at the mouth of the rectifying tower, then maintaining total reflux for 25-35 min, starting discharging, collecting the fraction to obtain methyl heptenone, and raising the temperature in the tower by 4-6 ℃ at the speed of 1.8-2.2 ℃/min when the methyl heptenone is about to be exhausted.
5. The method for extracting citronellal from litsea cubeba oil as claimed in claim 2, wherein in the step (3), the second stage of rectification comprises the following specific steps: after the methyl heptenone is discharged, slowly adjusting the vacuum degree in the rectifying tower to 0.09-0.11 MPa, heating the rectifying tower to 45-55 ℃ at the speed of 1.8-2.2 ℃/min by using heat conducting oil, enabling steam to appear at the mouth of the rectifying tower, then maintaining total reflux for 25-35 min, starting discharging, collecting fractions at the section to obtain citronellal, and raising the temperature in the rectifying tower to 4-6 ℃ at the speed of 1.8-2.2 ℃/min when the citronellal is about to be discharged completely.
6. The method for extracting citronellal from litsea cubeba oil as claimed in claim 2, wherein in the step (3), the third stage of rectification comprises the following specific steps: after the citronellal is completely discharged, heating the rectifying tower to 70-74 ℃ by using heat conduction oil at the speed of 1.8-2.2 ℃/min, enabling steam to appear at the mouth of the rectifying tower, then maintaining total reflux for 25-35 min, starting discharging, collecting fractions at the section to obtain citral, and when the citral is about to be discharged, heating the temperature in the rectifying tower to 4-6 ℃ at the speed of 1.8-2.2 ℃/min.
7. The method for extracting citronellal from litsea cubeba head oil as claimed in claim 1, wherein the litsea cubeba head oil is prepared by the following method: washing the fresh litsea cubeba fruits, placing the washed fresh litsea cubeba fruits in a distillation retort, adding water with the weight 1.5-2 times that of the litsea cubeba fruits, and extracting the fresh litsea cubeba fruits by adopting a volatile oil extractor to obtain crude oil of the litsea cubeba; adding the obtained crude oil of the litsea cubeba into a distillation flask, vacuumizing and distilling, controlling the vacuum degree to be 0.09-0.11 MPa and the top temperature of the distillation flask to be 45-55 ℃, and collecting fractions to obtain the litsea cubeba oil.
8. The method for extracting citronellal from litsea cubeba oil as claimed in claim 7, wherein the distillation tank uses 6-8 kg of pressure steam as a heating carrier; the reflux amount in the distillation tank is controlled to be 125-175L/h.
9. The method for extracting citronellal from litsea cubeba oil as claimed in any one of claims 1 to 8, wherein the drying agent used in the drying operation in step (2) is a neutral or weakly acidic drying agent selected from anhydrous magnesium sulfate or anhydrous calcium chloride.
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| 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 |
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| CN105237323B (en) * | 2015-10-20 | 2016-11-30 | 永州山香香料有限公司 | A kind of method extracting limonene from Fructus Litseae |
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