CN103044202A - Preparation method of alpha-terpilenol - Google Patents
Preparation method of alpha-terpilenol Download PDFInfo
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- CN103044202A CN103044202A CN2013100056214A CN201310005621A CN103044202A CN 103044202 A CN103044202 A CN 103044202A CN 2013100056214 A CN2013100056214 A CN 2013100056214A CN 201310005621 A CN201310005621 A CN 201310005621A CN 103044202 A CN103044202 A CN 103044202A
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Abstract
The invention discloses a preparation method of alpha-terpilenol, which comprises the steps that firstly, alpha-pinene, water and an organic solvent are placed in a container, and subjected to heating reflux; evaporated vapor enters a rectifying tower; secondly, a gas-phase mixture from the top of the rectifying tower enters a condenser at the top end of the rectifying tower; a condensed liquid enters a packed tower, and hydrated by the catalysis of a solid acid catalyst to form alpha-terpilenol; and finally, a mixed liquid of the packed tower enters the container and is evaporated continuously; the evaporated vapor enters the rectifying tower and separated; alpha-terpilenol is left in the rectifying tower; and a gas phase mixture from the top end of the rectifying tower continuously enters the condenser. The preparation method adopts a rectification-coupling technology, and takes alpha-pinene as a raw material, performs alpha-pinene hydration directly, and produces alpha-terpilenol continuously, the yield of alpha-terpilenol is increased; the selectivity of alpha-terpilenol is improved; the production capacity is improved; the energy consumption and the production cost are lowered; and compared with the traditional technology, the automatization of a production process is easy to realize.
Description
Technical field
The present invention relates to a kind of preparation method of alpha-terpineol.
Background technology
Terpineol 350 has another name called terpinol, the spices with stable Syringa oblata Lindl. fragrance, its fragrance can be given the people a kind of sensation that is in deep and remote woods with the breath of trees and flowers and plants, is widely used in the aspects such as pore forming material of the clear clean dose of ﹑ sterilant of spices essence ﹑ization woman's persona product ﹑ and flotation mineral.
The synthetic method of Terpineol 350, the program of being undertaken by reaction is divided into single stage method and two-step approach.Single stage method is that α-pinene direct hydration reaction under catalyst action generates Terpineol 350, and the method is with short production cycle, but Terpineol 350 yield Di ﹑ by product Duo ﹑ purity and fragrance are poor; Two step method is that α-pinene is under the acid catalyst effect, obtain first Terpine hydrate, obtain Terpineol 350 through the diluted acid catalytic dehydration again, the Terpineol 350 purity that the method is produced and fragrance are stable, and mature production technology, but alpha-terpineol content is lower, production cycle is long, energy consumption is high, and equipment corrosion is serious, and production cost is high.Kind by catalyst system therefor is divided, and can be divided into three major types, and the first kind is the liquid acid catalyzed process, comprises inorganic acid system, organic acid system, and inorganic-organic nitration mixture catalysis method, this method also is the representative of two-step approach, the strengths and weaknesses is as mentioned above; Equations of The Second Kind is the solid acid catalysis method, comprises the molecular sieve catalytic method, ion-exchange-resin process, and inorganic superpower acid system, heteropolyacid method etc., the method environmental friendliness, product is easily separated, but the selectivity of the transformation efficiency of α-pinene and alpha-terpineol is low, and not easily separated; The 3rd class is electrochemical process, adopts the cation electrode reaction in acetic acid and salt brine solution, can obtain the Terpineol 350 of racemization.
Liquid acid is apparent as the shortcoming of catalyzer, and ion exchange resin is used more and more extensive as catalyzer.Traditional method all is with catalyzer and raw material mixing one pot reaction, but the reaction of the synthetic alpha-terpineol of α-pinene is reversible reaction, namely alpha-terpineol can lose a part water and generate α-pinene under acidic conditions, the yield of the synthetic alpha-terpineol of one kettle way is not high, and solid acid catalyst is not suitable for tank reactor.There is recently patent report to synthesize L-terpineol with fixed-bed process.
Summary of the invention
The object of the invention is to: a kind of preparation method of alpha-terpineol is provided, and the method adopts the technique of rectifying-coupling to produce continuously alpha-terpineol take α-pinene as the raw material direct hydration, simplifies production technique, improves the product yield.
The technical solution that the present invention adopts is: at first, α-pinene, water and organic solvent in mass ratio 1:1 – 3:1 – 8 mixing place container, reflux, and the steam that evaporates enters rectifying tower; Secondly, out the gas phase mixture of α-pinene, water and organic solvent enters the condenser on rectifying tower top from the rectifying tower top, and the liquid that condensation is got off enters packing tower, and hydration generates alpha-terpineol under the catalysis of solid acid catalyst; At last, the mixed solution of α-pinene, water, organic solvent and alpha-terpineol enters and continues in the container to be evaporated, the steam that evaporates enters rectifying tower to be separated, alpha-terpineol is left in the rectifying tower, and the gas phase mixture that brings out the α-pinene, water and the organic solvent that come from rectifying tower top continues to enter condenser.
Wherein, described organic solvent is a kind of in methyl alcohol, ethanol, acetone, butanone, Virahol, the dioxane.
Wherein, described solid acid catalyst is the Zeo-karb of macroporous type, and Zeo-karb is a kind of in Amberlyst 35 Zeo-karbs, NKC-9 Zeo-karb, the D72 Zeo-karb.
Wherein, the temperature of packing tower body of the tower is 20-50 ℃, and the reaction times is 10-20h.
Wherein, filling BX screen waviness packings in the rectifying tower.
The present invention has the following advantages:
1, adopt fixed bed device, catalyzer separates with raw material, avoids the reversed reaction of alpha-terpineol;
2, the alpha-terpineol boiling point is high, and is separated during the alpha-terpineol of generation process rectifying tower in reaction process, only has the gas phase mixture of α-pinene, water and solvent composition to flow out the rectifying tower top, enters packing tower again and participate in reaction after condensation;
3, solid acid catalyst is Zeo-karb, and catalyzer is contained in the packing tower, and aftertreatment does not need separating catalyst, and is simple to operate, mild condition, and the reaction times is short, is fit to suitability for industrialized production.
4, catalyzer provided by the invention is easy to get, and cost is low, and capable of circulation applying mechanically has higher catalytic activity and chemo-selective.
Embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is restriction to technical scheme.
Embodiment 1: take by weighing respectively α-pinene (100g), deionized water (100g) and Virahol (100g) and place container, ebuillition of heated produces azeotrope, azeotropic stream enters packing tower through rectifying tower, condenser, and 20 ℃ of packing tower body of the tower temperature were reacted 20 hours; Wherein, the solid acid catalyst of packing tower is Amberlyst 35 Zeo-karbs.Sampling GC analyzes α-pinene transformation efficiency 92.8%, alpha-terpineol content 48.28%.
Embodiment 2: take by weighing respectively α-pinene (100g), deionized water (150g) and dioxane (300g) and place container, ebuillition of heated produces azeotrope, azeotropic stream enters packing tower through rectifying tower, condenser, and 25 ℃ of packing tower body of the tower temperature were reacted 18 hours; Wherein, the solid acid catalyst of packing tower is the NKC-9 Zeo-karb.Sampling GC analyzes α-pinene transformation efficiency 93.2%, alpha-terpineol content 48.52%.
Embodiment 3: take by weighing respectively α-pinene (100g), deionized water (200g) and acetone (450g) and place container, ebuillition of heated produces azeotrope, azeotropic stream enters packing tower through rectifying tower, condenser, and 30 ℃ of packing tower body of the tower temperature were reacted 15 hours; Wherein, the solid acid catalyst of packing tower is the D72 Zeo-karb.Sampling GC analyzes α-pinene transformation efficiency 94.8%, alpha-terpineol content 48.68%.
Embodiment 4: take by weighing respectively α-pinene (100g), deionized water (250g) and ethanol (600g) and place container, ebuillition of heated produces azeotrope, azeotropic stream enters packing tower through rectifying tower, condenser, and 40 ℃ of packing tower body of the tower temperature were reacted 12 hours; Wherein, the solid acid catalyst of packing tower is Amberlyst 35 Zeo-karbs.Sampling GC analyzes α-pinene transformation efficiency 96.8%, alpha-terpineol content 48.88%.
Embodiment 5: take by weighing respectively α-pinene (100g), deionized water (300g) and methyl alcohol (800g) and place container, ebuillition of heated produces azeotrope, azeotropic stream enters packing tower through rectifying tower, condenser, and packing tower body of the tower temperature 50 C reacted 10 hours; Wherein, the solid acid catalyst of packing tower is the NKC-9 Zeo-karb.Sampling GC analyzes α-pinene transformation efficiency 98.2%, alpha-terpineol content 49.58%.
Claims (5)
1. the preparation method of alpha-terpineol is characterized in that this preparation method may further comprise the steps: at first, α-pinene, water and organic solvent in mass ratio 1:1 – 3:1 – 8 mix and place container, reflux, and the steam that evaporates enters rectifying tower; Secondly, out the gas phase mixture of α-pinene, water and organic solvent enters the condenser on rectifying tower top from the rectifying tower top, and the liquid that condensation is got off enters packing tower, and hydration generates alpha-terpineol under the catalysis of solid acid catalyst; At last, the mixed solution of α-pinene, water, organic solvent and alpha-terpineol enters and continues in the container to be evaporated, the steam that evaporates enters rectifying tower to be separated, alpha-terpineol is left in the rectifying tower, and the gas phase mixture that brings out the α-pinene, water and the organic solvent that come from rectifying tower top continues to enter condenser.
2. the preparation method of alpha-terpineol according to claim 1 is characterized in that: wherein, described organic solvent is a kind of in methyl alcohol, ethanol, acetone, butanone, Virahol, the dioxane.
3. the preparation method of alpha-terpineol according to claim 1, it is characterized in that: wherein, described solid acid catalyst is the Zeo-karb of macroporous type, and Zeo-karb is a kind of in Amberlyst 35 Zeo-karbs, NKC-9 Zeo-karb, the D72 Zeo-karb.
4. the preparation method of alpha-terpineol according to claim 1, it is characterized in that: wherein, the temperature of packing tower body of the tower is 20-50 ℃, and the reaction times is 10-20h.
5. the preparation method of alpha-terpineol according to claim 1 is characterized in that: wherein, load the BX screen waviness packings in the rectifying tower.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285613A (en) * | 2013-05-08 | 2013-09-11 | 厦门大学 | Infinite reflux reaction distillation device of synthesizing terpineol and synthesizing method of device |
| CN104045519A (en) * | 2014-07-03 | 2014-09-17 | 宜宾石平香料有限公司 | High-purity Delta terpilenol separation and purification method |
| CN104230666A (en) * | 2014-08-26 | 2014-12-24 | 广西梧松林化集团有限公司 | Method for preparing terpineol from 3-carene |
| CN107253900A (en) * | 2017-06-09 | 2017-10-17 | 上海万香日化有限公司 | A kind of synthetic method of 2 pinanol |
| CN110054548A (en) * | 2019-04-11 | 2019-07-26 | 中国农业科学院兰州畜牧与兽药研究所 | A kind of method that solid acid concave convex rod catalyzes and synthesizes 4- terpinol |
| CN111359628A (en) * | 2020-02-19 | 2020-07-03 | 广西大学 | Preparation method of biomass solid acid catalyst and application of biomass solid acid catalyst in α -terpineol synthesis |
| EP3509737A4 (en) * | 2016-09-08 | 2020-08-19 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
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| CN1482113A (en) * | 2003-07-16 | 2004-03-17 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
| CN101108788A (en) * | 2007-07-13 | 2008-01-23 | 中国林业科学研究院林产化学工业研究所 | Method of manufacturing high purity alpha-terpineol |
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2013
- 2013-01-08 CN CN2013100056214A patent/CN103044202A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1482113A (en) * | 2003-07-16 | 2004-03-17 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
| CN101108788A (en) * | 2007-07-13 | 2008-01-23 | 中国林业科学研究院林产化学工业研究所 | Method of manufacturing high purity alpha-terpineol |
Non-Patent Citations (1)
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| GAODONG YANG ET AL.,: "Kinetic study of the direct hydration of turpentine", 《CHEMICAL ENGINEERING JOURNAL》, vol. 168, 31 December 2011 (2011-12-31) * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285613A (en) * | 2013-05-08 | 2013-09-11 | 厦门大学 | Infinite reflux reaction distillation device of synthesizing terpineol and synthesizing method of device |
| CN103285613B (en) * | 2013-05-08 | 2016-01-20 | 厦门大学 | A kind of total reflux reaction distilling apparatus and synthetic method thereof of synthesizing terpinol |
| CN104045519A (en) * | 2014-07-03 | 2014-09-17 | 宜宾石平香料有限公司 | High-purity Delta terpilenol separation and purification method |
| CN104045519B (en) * | 2014-07-03 | 2015-07-08 | 宜宾石平香料有限公司 | High-purity Delta terpilenol separation and purification method |
| CN104230666A (en) * | 2014-08-26 | 2014-12-24 | 广西梧松林化集团有限公司 | Method for preparing terpineol from 3-carene |
| EP3509737A4 (en) * | 2016-09-08 | 2020-08-19 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
| US11008271B2 (en) | 2016-09-08 | 2021-05-18 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
| CN107253900A (en) * | 2017-06-09 | 2017-10-17 | 上海万香日化有限公司 | A kind of synthetic method of 2 pinanol |
| CN107253900B (en) * | 2017-06-09 | 2021-07-16 | 上海万香日化有限公司 | Synthesis method of 2-pinanol |
| CN110054548A (en) * | 2019-04-11 | 2019-07-26 | 中国农业科学院兰州畜牧与兽药研究所 | A kind of method that solid acid concave convex rod catalyzes and synthesizes 4- terpinol |
| CN111359628A (en) * | 2020-02-19 | 2020-07-03 | 广西大学 | Preparation method of biomass solid acid catalyst and application of biomass solid acid catalyst in α -terpineol synthesis |
| CN111359628B (en) * | 2020-02-19 | 2023-06-06 | 广西大学 | Preparation method of biomass solid acid catalyst and application of biomass solid acid catalyst in synthesis of alpha-terpineol |
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Application publication date: 20130417 |