CN102850370A - Method for recovering 1,8-eucalyptol from eucalyptus oil by product - Google Patents
Method for recovering 1,8-eucalyptol from eucalyptus oil by product Download PDFInfo
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- CN102850370A CN102850370A CN2012102411998A CN201210241199A CN102850370A CN 102850370 A CN102850370 A CN 102850370A CN 2012102411998 A CN2012102411998 A CN 2012102411998A CN 201210241199 A CN201210241199 A CN 201210241199A CN 102850370 A CN102850370 A CN 102850370A
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Abstract
The invention discloses a method for recovering 1,8-eucalyptol from eucalyptus oil by products; the eucalyptus oil by products are subject to two-step rectification, wherein in the first step, phenol is added into the eucalyptus oil by products, and then reduced-pressure rectification is performed to obtain kettle bottom liquid; in the second step, water is added into the kettle bottom liquid, then normal pressure rectification is performed to obtain an azeotrope of 1,8-eucalyptol and water; a water layer of the azeotrope is removed by layering; the azeotrope is dried to obtain the 1,8-eucalyptol product. The method of the invention provides a 1,8-eucalyptol recovery rate of more than 70% and a purity of more than 98%, and has the advantages of simple operation, short rectification time, high recovery rate, green and environmental protection, and suitability for industrial application.
Description
Technical field
The present invention relates to a kind of method that from the eucalyptus oil substandard goods, reclaims 1,8-eucalyptol, 1 of preparation, the 8-eucalyptol can be used as spices and essence and is used for food or daily-use chemical industry industry, also can be used for field of medicaments.
Background technology
Eucalyptus oil is eucalyptus leaves oil droplet emiocytosis volatile oil out, is one of the world's ten large essential oils, has unique fragrance and multiple biological activity, is widely used in daily-use chemical industry, food, medicine and other fields.The folium eucalypti main body of oil is 1,8-eucalyptol.1, the 8-eucalyptol has camphor sample fragrance, both can be used for the allotment of edible and daily essence, it also is the main pharmacodynamics composition in the medicine, can play the effect of antibiotic, anti-inflammatory, desinsection, research in recent years shows that 1,8-eucalyptus oil have the effect of good inhibition Leukocyte Growth, and this gives its larger using value and development space.
The eucalyptus oil industrial production is to obtain crude eucalyptus oil with the branches and leaves of eucalyptus with the steam distillation distillation, obtain folium eucalypti hair oil (mainly containing firpene) through rectifying separation, the products such as eucalyptus leaf essential oil (containing 80wt%1, the 8-eucalyptol), 40w% Terpineol 350, pin oil (after the rectifying in tower reactor remaining raffinate be pin oil).Then eucalyptus leaf essential oil (containing 80wt%1, the 8-eucalyptol) is further purified and obtain 1 of 99wt%, 8-eucalyptol.The comparatively ripe method of industrial application is to use the refrigerated centrifugation of the reports such as Zheng Xun method 80% eucalyptus oil separation and purification to be obtained 1 more than the 99wt%, the 8-eucalyptol.The method at first with content 80wt% eucalyptus oil at the lower freezing 48h of low temperature-20 ℃, be the centrifugal rejection filter of supercentrifuge of 1200r/min afterwards with rotating speed, be product after the gained solid dissolves, yield can reach 42%.
By above-mentioned technical process, although can obtain 1 of higher degree, 8-eucalyptol product, but produced a large amount of eucalyptus oil byproducts, can obtain Terpineol 350 cut (alpha-terpineol that contain 40wt%) and pin wet goods byproduct in the time of (containing 80wt%1, the 8-eucalyptol) such as: crude eucalyptus oil stage of rectification obtaining eucalyptus leaf essential oil; And the frozen centrifugation purification eucalyptus leaf essential oil stage also can produce a large amount of mother liquors when obtaining the highly pure eucalyptus oil element.Be rich in the components such as alpha-terpineol, terpinene-4-alcohol and terpinyl acetate in the Terpineol 350 cut, in pin oil, mother liquor, contain a large amount of eucalyptols, limonene, the natural components such as p-cymene hydrocarbon, γ-terpinene.
And these eucalyptus oil byproducts both had been not easy to sell, and also were difficult for processing, and gave producer's economic loss, increased its production cost, had also wasted natural resource.Thus, how to process the eucalyptus oil substandard goods, make it obtain comprehensive effectively utilization, become problem demanding prompt solution.
Because 1,8-eucalyptol, limonene, isopropyltoluene three boiling point are close, adopt the conventional distillation method to be difficult to be recovered to higher degree 1,8-eucalyptol from the eucalyptus oil substandard goods.In the prior art; although Davis and Tan Xinzhi etc. have reported that the acidic solution that forms take sulfuric acid and phosphoric acid is as extraction agent; from the eucalyptus oil substandard goods, reclaim eucalyptol (US3923837; CN8610884); but the defective that this method exists is that operation steps is many; a large amount of spent acid solution dischargings is arranged, be unfavorable for suitability for industrialized production, also be unfavorable for environment protection.
Summary of the invention
For addressing this problem, the present invention has taked following technical scheme:
A kind of method that from the eucalyptus oil substandard goods, reclaims 1,8-eucalyptol, through two step rectifying, the first step: add phenol in the eucalyptus oil substandard goods, phenol usage and feed liquid mass ratio are 0.3: 1～4: 1 with the eucalyptus oil substandard goods; Rectification under vacuum distillates imurity-removal when the tower top temperature scope is 45～80 ℃, the time of removing is 1～6h, stops rectifying, gets kettle base solution; Second step: add water in the kettle base solution, atmospheric distillation accesses the cut of 90～100 ℃ of tower top temperature scopes, and the time of accessing is 1～6h, and the gained cut is the azeotrope of 1,8-eucalyptol and water, the azeotrope branch vibration layer, and drying gets 1,8-eucalyptol.
Described eucalyptus oil substandard goods are that eucalyptus leaf essential oil (contains 80wt%1, the 8-eucalyptol) prepares high-purity (＞99wt%) 1 through the frozen centrifugation technology, the mother liquor that produces during the 8-eucalyptol, or eucalyptus oil crude oil rectifying separation eucalyptus leaf essential oil (contains 80wt%1, the 8-eucalyptol) the pin oil that produces the time (after the rectifying in the tower reactor remaining raffinate be pin oil), in the eucalyptus oil substandard goods 1,8-eucalyptol content＞30wt%.
Described pin oil refers to after the rectifying remaining raffinate in the tower reactor, and described mother liquor is that frozen centrifugation separates and removes the remaining liquid of solid.Described tower top temperature is the boiling range that component distillates from system, describedly removes the time, for impurity composition heats up in a steamer the most time substantially from beginning to distillate.
A kind of method that from the eucalyptus oil substandard goods, reclaims 1,8-eucalyptol of the present invention, rectification under vacuum described in the first step, pressure is 0.5～4kPa; The first step rectification under vacuum is to get kettle base solution for imurity-removal, described impurity is mainly firpene, limonene, to compounds such as poly-loose flower hydrocarbon, when 45～80 ℃ of tower top temperature scopes, firpene, limonene, the impurity such as poly-loose flower hydrocarbon will be distillated from system, this distillates process and is and makes impurity removal, these impurity heat up in a steamer to the greatest extent substantially in 1～6h, and the time that namely removes is 1～6h.
A kind of method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods of the present invention, phenol described in the first step rectification under vacuum, its consumption be generally 0.3: 1 with the quality of material ratio～and 4: 1; In phenol usage and the material 1,8-eucalyptol content is relevant, and the higher consumption of content is more; The adding of phenol can be in the phenol adding material, also can be material and adds in the phenol, and before the rectification under vacuum, heated and stirred approximately 0.5～1h makes phenol fully mix better effects if with material.
Of the present inventionly a kind ofly from the eucalyptus oil substandard goods, reclaim 1, the method of 8-eucalyptol, phenol described in the first step can be sterling phenol, also can be in this patent method second step rectification process gained phenol raffinate or the phenol raffinate is further processed gained to contain phenol product.
A kind of method that from the eucalyptus oil substandard goods, reclaims 1,8-eucalyptol of the present invention, kettle base solution adds water described in the second step, and water consumption and kettle base solution mass ratio are 1: 1～3: 1; Described branch vibration layer can be by leaving standstill, or adopt separating funnel to carry out, and gets oil reservoir and add the siccative commonly used such as anhydrous sodium sulphate and process, and gets 1,8-eucalyptol product.
A kind of method that from the eucalyptus oil substandard goods, reclaims 1,8-eucalyptol of the present invention, atmospheric distillation described in the second step, the first step that can continue rectifying is directly carried out, and also kettle base solution can be imported on the other cover rectifier unit to carry out.
A kind of method that from the eucalyptus oil substandard goods, reclaims 1,8-eucalyptol of the present invention, the kettle base solution main component is phenol after the second step rectifying, this kettle base solution reclaims can directly do the first step rectifying usefulness, also can do the first step rectifying through certain processing.
Of the present invention 1,8-eucalyptol product can be used as spices and essence and is used for food or daily-use chemical industry industry, also can be used for field of medicaments.
Of the present inventionly a kind ofly from the eucalyptus oil substandard goods, reclaim 1, in the method for 8-eucalyptol, the effect of the first step, phenol is equivalent to extraction agent, utilize in itself and the eucalyptol Binding change system characteristics of relative volatility between component, remove the hydro carbons major impurities such as firpene, isopropyltoluene, limonene, phenol and eucalyptol or hydrocarbon impurities not azeotropic distillate; Second step, atmospheric distillation, 1,8-eucalyptol and water form azeotrope and distillate, and phenol is stayed at the bottom of the still.This patent has overcome existing methodical shortcoming and defect, has a discharging of waste liquid few, and the rectifying time is short, and the rate of recovery is high, is easy to industrialized advantage.Through 1 of two step rectifying gained, 8-eucalyptol product, the rate of recovery＞70%, purity＞98%.
Embodiment
Embodiment 1
In the heating kettle that distilling filled tower (30 of stage number) is housed, add 1210 parts of phenol, 2150 parts of eucalyptus oil substandard goods (1,8-eucalyptol content 37wt%), keep system pressure 2.4kPa, heated and stirred 0.5h, behind the total reflux 40min, regulating reflux ratio is 2: 2, removes the impurity compositions such as firpene, limonene, p-cymene hydrocarbon in still top temperature is 52～70 ℃ of scopes, remove time 2h, stop rectifying, cooling gets 2432 parts of kettle base solutions.
Utilize this rectifier unit to continue experiment.In the gained kettle base solution, add 2500 parts of tap water, total reflux 1h, regulating reflux ratio is 2: 2, accesses the cut that tower top temperature is 96～98 ℃ of scopes, accesses time 3h, stops rectifying.The gained cut places separating funnel, and branch vibration layer is got oil reservoir, and anhydrous sodium sulfate drying gets 560 parts of 1,8-eucalyptols, purity 99.2%, the rate of recovery 70.5%.
Embodiment 2
In the heating kettle that distilling filled tower (50 of stage number) is housed, add 1720 parts of phenol, 2150 parts of eucalyptus oil substandard goods (1,8-eucalyptol content 45wt%), keep system pressure 3.2kPa, heated and stirred 0.5h, behind the total reflux 50min, regulating reflux ratio is 4: 1, removes the impurity compositions such as firpene, limonene, p-cymene hydrocarbon in still top temperature is 55～68 ℃ of scopes, remove time 5h, stop rectifying, cooling gets 2840 parts of kettle base solutions.
Utilize this rectifier unit to continue experiment.In the gained kettle base solution, add 3000 parts of tap water, total reflux 1h, regulating reflux ratio is 2: 2, accesses the cut that tower top temperature is 95～100 ℃ of scopes, accesses time 2h, stops rectifying.The gained cut is poured in the elongated beaker and is left standstill, and the layer that anhydrates that slowly inclines is got oil reservoir, and anhydrous sodium sulfate drying gets 726 parts of 1,8-eucalyptols, purity 99.2%, the rate of recovery 75%.
Embodiment 3
In the heating kettle that distilling filled tower (70 of stage number) is housed, add 1500 parts of phenol, 1500 parts of eucalyptus oil substandard goods (1,8-eucalyptol content 50wt%), keep system pressure 4.0kPa, heated and stirred 40min, total reflux 1h, regulating reflux ratio is 2: 2, removes the impurity compositions such as firpene, limonene, p-cymene hydrocarbon in tower top temperature is 50～75 ℃ of scopes, remove time 1.5h, stop rectifying, cooling gets 2300 parts of kettle base solutions.
Use kettle base solution instead another set of rectifier unit (20 of stage number) and continue experiment.In the gained kettle base solution, add 4000 parts of tap water, total reflux 50min, regulating reflux ratio is 2: 2, accesses the cut of 92～100 ℃ of scopes of still top temperature, accesses time 2.5h, stops rectifying.The gained cut is poured in the separating funnel, gets oil reservoir, and Calcium Chloride Powder Anhydrous is dry, gets 585 parts of 1,8-eucalyptols, purity 99.9%, the rate of recovery 78%.
Embodiment 4
In the heating kettle that distilling filled tower (80 of stage number) is housed, add 1000 parts of phenol, 2000 parts of eucalyptus oil substandard goods (1,8-eucalyptol content 32wt%), keep system pressure 3.0kPa, heated and stirred 40min, total reflux 1h, regulating reflux ratio is 2: 2, removes the impurity compositions such as limonene, p-cymene hydrocarbon in tower top temperature is 49～78 ℃ of scopes, remove time 6h, stop rectifying, cooling gets 1680 parts of kettle base solutions.
Use kettle base solution instead another set of rectifier unit (20 of stage number) and continue experiment.In the gained kettle base solution, add 1800 parts of tap water, total reflux 1h, regulating reflux ratio is 2: 2, accesses the cut of 94～100 ℃ of scopes of tower top temperature, accesses time 1.5h, stops rectifying.The gained cut is poured in the separating funnel, gets oil reservoir, and Calcium Chloride Powder Anhydrous is dry, gets 454 parts of 1,8-eucalyptols, purity 98.9%, the rate of recovery 71%.
Claims (7)
1. method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods is characterized in that: through two step rectifying, the first step: add phenol in the eucalyptus oil substandard goods, phenol usage and feed liquid mass ratio are 0.3: 1～4: 1 with the eucalyptus oil substandard goods; Then carry out rectification under vacuum, imurity-removal when the tower top temperature scope is 45～80 ℃, the time of removing is 1～6h, gets kettle base solution; Second step: add water in kettle base solution, atmospheric distillation accesses the cut of 90～100 ℃ of tower top temperatures, and the time of accessing is 1～6h, gained cut branch vibration layer, and drying gets 1,8-eucalyptol; Described eucalyptus oil substandard goods, its 1,8-eucalyptol content＞30wt%.
2. a kind of method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods according to claim 1, it is characterized in that: the pressure of the first step rectification under vacuum is 0.5～4kPa.
3. a kind of method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods according to claim 1, it is characterized in that: the add-on of second step atmospheric distillation water and kettle base solution mass ratio are 1: 1～3: 1.
4. a kind of method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods according to claim 1 is characterized in that: 1, the 8-eucalyptol rate of recovery＞70%, purity＞98%.
5. a kind of method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods according to claim 1, it is characterized in that: before the first step rectifying, heated and stirred 0.5～1h makes phenol fully mix with material.
6. according to claim 1ly a kind ofly from the eucalyptus oil substandard goods, reclaim 1, the method of 8-eucalyptol is characterized in that: described phenol is sterling phenol or second step rectification process gained phenol raffinate or the phenol raffinate is further processed gained contains phenol product.
7. a kind of method that reclaims 1,8-eucalyptol from the eucalyptus oil substandard goods according to claim 1 is characterized in that: described branch vibration layer is by leaving standstill, or adopts separating funnel to carry out, and dryly adds the siccative processing for getting oil reservoir.
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| CN201210241199.8A CN102850370B (en) | 2012-07-13 | 2012-07-13 | A kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods |
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| CN201210241199.8A CN102850370B (en) | 2012-07-13 | 2012-07-13 | A kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540969A (en) * | 2015-12-16 | 2016-05-04 | 广东工业大学 | High-phenol concentration waste water treatment method |
| CN105820035A (en) * | 2016-04-21 | 2016-08-03 | 广东工业大学 | Method for utilizing cycloalkanol in eucalyptol separation water solution and application of cycloalkanol |
| CN106554360A (en) * | 2016-11-21 | 2017-04-05 | 四川省林业科学研究院 | A kind of method of 1,8 Cineoles in purification yusho oil |
| CN106831335A (en) * | 2017-01-21 | 2017-06-13 | 云南国润香料制造有限公司 | A kind of technique of 4 terpinenol isolated from eucalyptus oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540969A (en) * | 2015-12-16 | 2016-05-04 | 广东工业大学 | High-phenol concentration waste water treatment method |
| CN105820035A (en) * | 2016-04-21 | 2016-08-03 | 广东工业大学 | Method for utilizing cycloalkanol in eucalyptol separation water solution and application of cycloalkanol |
| CN106554360A (en) * | 2016-11-21 | 2017-04-05 | 四川省林业科学研究院 | A kind of method of 1,8 Cineoles in purification yusho oil |
| CN106831335A (en) * | 2017-01-21 | 2017-06-13 | 云南国润香料制造有限公司 | A kind of technique of 4 terpinenol isolated from eucalyptus oil |
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Inventor after: Xie Jianchun Inventor after: Wang Shi Inventor after: Li Youhong Inventor before: Xie Jianchun Inventor before: Wang Shi Inventor before: Sun Baoguo Inventor before: Li Youhong Inventor before: Zheng Fuping Inventor before: Sun Jinyuan Inventor before: Huang Mingquan |
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