CN102850370B - A kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods - Google Patents
A kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods Download PDFInfo
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- CN102850370B CN102850370B CN201210241199.8A CN201210241199A CN102850370B CN 102850370 B CN102850370 B CN 102850370B CN 201210241199 A CN201210241199 A CN 201210241199A CN 102850370 B CN102850370 B CN 102850370B
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Abstract
The invention discloses a kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods, by eucalyptus oil substandard goods, through two step rectifying, the first step: add phenol in eucalyptus oil substandard goods, then carry out rectification under vacuum, obtain kettle base solution; Second step: in kettle base solution, add water, then carry out atmospheric distillation, obtain the azeotropic mixture of 1,8-cineole and water, azeotropic mixture branch vibration layer, dry, obtain 1,8-cineole product. This patent method, 1,8-cineole rate of recovery > 70%, purity > 98%, has simple to operately, and the rectifying time is short, and the rate of recovery is high, environmental protection, advantage that can industrial applications.
Description
Technical field
The present invention relates to a kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods, 1 of preparation, 8-cineole, can be used as spices and essence 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 biologically active, is widely used in daily-use chemical industry, food, medicine and other fields. Folium eucalypti main body of oil is 1,8-cineole. 1,8-cineole has camphor sample fragrance, both can be used for the allotment of edible and daily essence, also be the main pharmacodynamics composition in medicine, can play the effect of antibacterial, 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.
Eucalyptus oil industrial production is to obtain crude eucalyptus oil with the branches and leaves of eucalyptus with steam distillation distillation, separate and obtain folium eucalypti hair oil (mainly containing firpene) through rectifying, the products such as eucalyptus leaf essential oil (containing 80wt%1,8-cineole), 40w% terpinol, pin oil (after rectifying, remaining raffinate is pin oil in tower reactor). Then eucalyptus leaf essential oil (containing 80wt%1,8-cineole) is further purified and obtained 1 of 99wt%, 8-cineole. 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 to more than 99wt% 1,8-cineole. The method is first by content 80wt% eucalyptus oil freezing 48h at low temperature-20 DEG C, and the centrifugal rejection filter of supercentrifuge that is 1200r/min with rotating speed afterwards, is product after gained solid dissolves, and yield can reach 42%.
By above-mentioned technological process, although can obtain 1 of higher degree, 8-cineole product, but produced a large amount of eucalyptus oil byproducts, as: crude eucalyptus oil stage of rectification can obtain terpinol cut (containing the alpha-terpineol of 40wt%) and pin wet goods byproduct in the time obtaining eucalyptus leaf essential oil (containing 80wt%1,8-cineole); And the refrigerated centrifuge purification eucalyptus leaf essential oil stage also can produce a large amount of mother liquors in obtaining highly pure eucalyptus oil element. In terpinol cut, be rich in the components such as alpha-terpineol, terpinene-4-alcohol and terpinyl acetate, in pin oil, mother liquor, contain a large amount of cineoles, citrene, the natural components such as p-cymene hydrocarbon, γ-terpinene.
And these eucalyptus oil byproducts had both been not easy to sell, be also difficult for processing, cause economic loss to producer, increase its production cost, also waste natural resources. Thus, how to process eucalyptus oil substandard goods, make it obtain comprehensive effectively utilization, become problem demanding prompt solution.
Because 1,8-cineole, citrene, cymene three boiling point are close, adopt conventional distillation method to be difficult to be recovered to higher degree 1,8-cineole from eucalyptus oil substandard goods. In prior art; although Davis and Tan Xinzhi etc. have reported that acid solution taking sulfuric acid and phosphoric acid composition is as extractant; from eucalyptus oil substandard goods, reclaim cineole (US3923837; CN8610884); but the defect that the method exists is that operating procedure is many; there is a large amount of acid pickle discharges, be unfavorable for suitability for industrialized production, be also unfavorable for environmental protection.
Summary of the invention
For addressing this problem, the present invention has taked following technical scheme:
A kind of method that reclaims 1,8-cineole from eucalyptus oil substandard goods, by eucalyptus oil substandard goods through two step rectifying, the first step: add phenol in eucalyptus oil substandard goods, phenol usage and feed liquid mass ratio are 0.3: 1～4: 1; Rectification under vacuum distillates imurity-removal in the time that tower top temperature scope is 45～80 DEG C, and the time of removing is 1～6h, stops rectifying, obtains kettle base solution; Second step: add water in kettle base solution, atmospheric distillation, accesses the cut of 90～100 DEG C of tower top temperature scopes, and the time of accessing is 1～6h, and gained cut is the azeotropic mixture of 1,8-cineole and water, and azeotropic mixture branch vibration layer is dry, obtains 1,8-cineole.
Described eucalyptus oil substandard goods are that eucalyptus leaf essential oil is (containing 80wt%1,8-cineole) prepare high-purity (> 99wt%) 1 through refrigerated centrifuge technology, the mother liquor producing when 8-cineole, or the rectifying of eucalyptus oil crude oil separates eucalyptus leaf essential oil (containing 80wt%1,8-cineole) time produce pin oil (after rectifying, in tower reactor, remaining raffinate is pin oil), in eucalyptus oil substandard goods 1,8-cineole content > 30wt%.
Described pin oil refers to after rectifying remaining raffinate in tower reactor, and described mother liquor is that refrigerated centrifuge separates and removes the remaining liquid of solid. Described tower top temperature is the boiling range that component distillates from system, described in remove the time, for impurity composition heats up in a steamer the most time substantially from starting to distillate.
One of the present invention reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, rectification under vacuum described in the first step, and pressure is 0.5～4kPa; First step rectification under vacuum is to obtain kettle base solution for imurity-removal, described impurity is mainly firpene, citrene, to compounds such as poly-loose flower hydrocarbon, in the time of 45～80 DEG C of tower top temperature scopes, firpene, citrene, the impurity such as poly-loose flower hydrocarbon will be distillated from system, this distillates process and is and makes impurity removal, in 1～6h, these impurity heat up in a steamer to the greatest extent substantially, and the time that removes is 1～6h.
One of the present invention reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, phenol described in first step rectification under vacuum, and its consumption is generally 0.3: 1 with quality of material ratio～and 4: 1; In phenol usage and material 1,8-cineole content is relevant, and the higher consumption of content is more; The adding of phenol can be phenol and add in material, also can be material and add in phenol, before rectification under vacuum, heating stir about 0.5～1h makes phenol fully mix with material, better effects if.
One of the present invention reclaims 1 from eucalyptus oil substandard goods, the method of 8-cineole, 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 phenol raffinate is further processed to gained containing phenol product.
One of the present invention reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, and described in second step, kettle base solution adds water, and water consumption and kettle base solution mass ratio are 1: 1～3: 1; Described branch vibration layer can pass through to leave standstill, or adopts separatory funnel to carry out, and gets oil reservoir and adds the conventional drier processing such as anhydrous sodium sulfate, obtains 1,8-cineole product.
One of the present invention reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, atmospheric distillation described in second step, and the first step that can continue rectifying is directly carried out, and also kettle base solution can be imported on other a set of rectifier unit and carry out.
One of the present invention reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, and after second step rectifying, kettle base solution main component is phenol, and this kettle base solution reclaims can directly do first step rectifying use, also can do first step rectifying through certain processing.
Of the present invention 1,8-cineole product, can be used as spices and essence for food or daily-use chemical industry industry, also can be used for field of medicaments.
One of the present invention reclaims 1 from eucalyptus oil substandard goods, in the method for 8-cineole, the effect of the first step, phenol is equivalent to extractant, utilize in itself and cineole Binding change system the feature of relative volatility between component, remove the hydro carbons major impurities such as firpene, cymene, citrene, phenol and cineole or hydrocarbon impurities not azeotropic distillate; Second step, atmospheric distillation, 1,8-cineole and water form azeotropic mixture and distillate, at the bottom of phenol is stayed still. This patent has overcome existing methodical shortcoming and defect, has 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-cineole product, rate of recovery > 70%, purity > 98%.
Detailed description of the invention
Embodiment 1
Being equipped with in the heating kettle of distilling filled tower (30 of the numbers of plates), add 1210 parts of phenol, 2150 parts of eucalyptus oil substandard goods (1,8-cineole content 37wt%), maintain system pressure 2.4kPa, add thermal agitation 0.5h, after infinite reflux 40min, regulating reflux ratio is 2: 2, is within the scope of 52～70 DEG C, to remove the impurity compositions such as firpene, citrene, p-cymene hydrocarbon in still top temperature, remove time 2h, stop rectifying, cooling, obtain 2432 parts of kettle base solutions.
Utilize this rectifier unit to continue experiment. In gained kettle base solution, add 2500 parts of running water, infinite reflux 1h, regulating reflux ratio is 2: 2, accesses the cut that tower top temperature is 96～98 DEG C of scopes, accesses time 3h, stops rectifying. Gained cut is placed in separatory funnel, and branch vibration layer is got oil reservoir, and anhydrous sodium sulfate drying obtains 560 parts of 1,8-cineoles, purity 99.2%, the rate of recovery 70.5%.
Embodiment 2
Being equipped with in the heating kettle of distilling filled tower (50 of the numbers of plates), add 1720 parts of phenol, 2150 parts of eucalyptus oil substandard goods (1,8-cineole content 45wt%), maintain system pressure 3.2kPa, add thermal agitation 0.5h, after infinite reflux 50min, regulating reflux ratio is 4: 1, is within the scope of 55～68 DEG C, to remove the impurity compositions such as firpene, citrene, p-cymene hydrocarbon in still top temperature, remove time 5h, stop rectifying, cooling, obtain 2840 parts of kettle base solutions.
Utilize this rectifier unit to continue experiment. In gained kettle base solution, add 3000 parts of running water, infinite reflux 1h, regulating reflux ratio is 2: 2, accesses the cut that tower top temperature is 95～100 DEG C of scopes, accesses time 2h, stops rectifying. Gained cut is poured in elongated beaker and is left standstill, and the layer that anhydrates that slowly inclines, gets oil reservoir, and anhydrous sodium sulfate drying obtains 726 parts of 1,8-cineoles, purity 99.2%, the rate of recovery 75%.
Embodiment 3
Being equipped with in the heating kettle of distilling filled tower (70 of the numbers of plates), add 1500 parts of phenol, 1500 parts of eucalyptus oil substandard goods (1,8-cineole content 50wt%), maintain system pressure 4.0kPa, add thermal agitation 40min, infinite reflux 1h, regulating reflux ratio is 2: 2, is within the scope of 50～75 DEG C, to remove the impurity compositions such as firpene, citrene, p-cymene hydrocarbon in tower top temperature, remove time 1.5h, stop rectifying, cooling, obtain 2300 parts of kettle base solutions.
Use kettle base solution instead another set of rectifier unit (20 of the numbers of plates) and continue experiment. In gained kettle base solution, add 4000 parts of running water, infinite reflux 50min, regulating reflux ratio is 2: 2, accesses the cut of 92～100 DEG C of scopes of still top temperature, accesses time 2.5h, stops rectifying. Gained cut is poured in separatory funnel, gets oil reservoir, and anhydrous calcium chloride is dry, obtains 585 parts of 1,8-cineoles, purity 99.9%, the rate of recovery 78%.
Embodiment 4
Being equipped with in the heating kettle of distilling filled tower (80 of the numbers of plates), add 1000 parts of phenol, 2000 parts of eucalyptus oil substandard goods (1,8-cineole content 32wt%), maintain system pressure 3.0kPa, add thermal agitation 40min, infinite reflux 1h, regulating reflux ratio is 2: 2, is within the scope of 49～78 DEG C, to remove the impurity composition such as citrene, p-cymene hydrocarbon in tower top temperature, remove time 6h, stop rectifying, cooling, obtain 1680 parts of kettle base solutions.
Use kettle base solution instead another set of rectifier unit (20 of the numbers of plates) and continue experiment. In gained kettle base solution, add 1800 parts of running water, infinite reflux 1h, regulating reflux ratio is 2: 2, accesses the cut of 94～100 DEG C of scopes of tower top temperature, accesses time 1.5h, stops rectifying. Gained cut is poured in separatory funnel, gets oil reservoir, and anhydrous calcium chloride is dry, obtains 454 parts of 1,8-cineoles, purity 98.9%, the rate of recovery 71%.
Claims (6)
1. one kind is reclaimed the method for 1,8-cineole from eucalyptus oil substandard goods, it is characterized in that: by eucalyptus oil substandard goods through two step rectifying, the first step: add phenol in eucalyptus oil substandard goods, phenol usage and feed liquid mass ratio are 0.3: 1～4: 1; Then carry out rectification under vacuum, imurity-removal in the time that tower top temperature scope is 45～80 DEG C, the time of removing is 1～6h, obtains kettle base solution; Second step: add water in kettle base solution, atmospheric distillation, accesses the cut of 90～100 DEG C of tower top temperatures, and the time of accessing is 1～6h, and gained cut branch vibration layer is dry, obtains 1,8-cineole; Before first step rectifying, add thermal agitation 0.5～1h phenol is fully mixed with material; Described eucalyptus oil substandard goods, its 1,8-cineole content > 30wt%.
2. one according to claim 1 reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, it is characterized in that: the pressure of first step rectification under vacuum is 0.5～4kPa.
3. one according to claim 1 reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, it is characterized in that: the addition of second step atmospheric distillation water and kettle base solution mass ratio are 1: 1～3: 1.
4. one according to claim 1 reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, it is characterized in that: 1,8-cineole rate of recovery > 70%, purity > 98%.
5. one according to claim 1 reclaims 1 from eucalyptus oil substandard goods, the method of 8-cineole, is characterized in that: described phenol is sterling phenol or second step rectification process gained phenol raffinate or phenol raffinate is further processed to gained containing phenol product.
6. one according to claim 1 reclaims the method for 1,8-cineole from eucalyptus oil substandard goods, it is characterized in that: described branch vibration layer passes through to leave standstill, or adopts separatory funnel to carry out, and is dried as getting oil reservoir and adds drier processing.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN105540969B (en) * | 2015-12-16 | 2018-08-17 | 广东工业大学 | A kind of processing method of the waste water containing high-concentration phenol |
| CN105820035B (en) * | 2016-04-21 | 2018-05-15 | 广东工业大学 | A kind of method and its application that cyclic alkanol in aqueous solution is separated using Cineole |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2090620A (en) * | 1936-09-08 | 1937-08-24 | Newport Ind Inc | Method of separating cineols from hydrocarbons of similar boiling range |
| US2459432A (en) * | 1948-08-20 | 1949-01-18 | Hercules Powder Co Ltd | Separation of cineoles from hydrocarbons of similar boiling range by azeotropic distillation with phenols |
| US3923837A (en) * | 1974-10-15 | 1975-12-02 | American Cyanamid Co | Extraction and recovery of cineole |
| EP0125539A2 (en) * | 1983-05-12 | 1984-11-21 | Union Camp Corporation | Separation of 1,8-cineole |
| CN86108040A (en) * | 1986-12-06 | 1988-06-22 | 湛江医学院 | Process for recoverying eucalyptus oil |
| CN102504955A (en) * | 2011-11-01 | 2012-06-20 | 昆明理工大学 | Processing for extracting and purifying eucalyptus oil |
-
2012
- 2012-07-13 CN CN201210241199.8A patent/CN102850370B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2090620A (en) * | 1936-09-08 | 1937-08-24 | Newport Ind Inc | Method of separating cineols from hydrocarbons of similar boiling range |
| US2459432A (en) * | 1948-08-20 | 1949-01-18 | Hercules Powder Co Ltd | Separation of cineoles from hydrocarbons of similar boiling range by azeotropic distillation with phenols |
| US3923837A (en) * | 1974-10-15 | 1975-12-02 | American Cyanamid Co | Extraction and recovery of cineole |
| EP0125539A2 (en) * | 1983-05-12 | 1984-11-21 | Union Camp Corporation | Separation of 1,8-cineole |
| CN86108040A (en) * | 1986-12-06 | 1988-06-22 | 湛江医学院 | Process for recoverying eucalyptus oil |
| CN102504955A (en) * | 2011-11-01 | 2012-06-20 | 昆明理工大学 | Processing for extracting and purifying eucalyptus oil |
Non-Patent Citations (3)
| Title |
|---|
| 1,8-桉叶油素的研究进展;王文元等;《食品与药品》;20071231;第9卷(第02A期);第56页-59页 * |
| 从桉叶油副产品中间歇精馏纯化α-松油醇;王石等;《精细化工》;20120116;第29卷(第2期);第134-139页 * |
| 助剂辅助真空间歇精馏分离1,8-桉叶素;张健生等;《化工进展》;20111231;第30卷(第S1期);第107-110页 * |
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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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