CN103449954B - Preparation method of high-purity longifolene - Google Patents
Preparation method of high-purity longifolene Download PDFInfo
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- CN103449954B CN103449954B CN201310377927.2A CN201310377927A CN103449954B CN 103449954 B CN103449954 B CN 103449954B CN 201310377927 A CN201310377927 A CN 201310377927A CN 103449954 B CN103449954 B CN 103449954B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of high-purity longifolene. The preparation method comprises the following steps: placing mixture of 65-70 percent by weight of longifolene and 10-30 percent by weight of caryophyllene into a reaction container; adding a catalyst to perform caryophyllene polymerization reaction, wherein the reaction heating temperature is 80-110 DEG C and the reaction time is 3-6 hours; filtering; recovering the catalyst; performing reduced pressure distillation; rectifying to obtain the longifolene finished product with content of 85-95 percent, wherein the catalyst is macroporous weakly acidic acrylic acid cation exchange resin D113; the weight ratio of the mixture to the catalyst is 1:0.05-0.1. Compared with the prior art, the preparation method has the advantage that the problems of difficulty in separation of the high-purity longifolene and high production cost existing in the prior art can be solved.
Description
Technical field
The present invention relates to chemical industry rosin deep process technology field, especially a kind of preparation method that can become more readily available the longifolene of high-content.
Background technology
At present, the purification of the longifolene in turps heavy oil is generally realized by underpressure distillation, and underpressure distillation is difficult to be purified to more than 80% longifolene, reason is the composition containing a kind of caryophyllene in heavy oil, the boiling point of caryophyllene and physical property are with longifolene closely, the content of caryophyllene and the content ratio of longifolene according to different tree kinds between 1:3 ~ 4, be difficult to by the method for fractionation, both be separated, so carry out underpressure distillation without the turps heavy oil processed can only distill the longifolene obtaining 65% ~ 70% content.Meet customer requirement raising longifolene content must adopt new technological invention to realize.
Summary of the invention
The invention provides a kind of preparation method of high-purity longifolene, produce the not high problem of acquisition longifolene product content to solve existing longifolene.
In order to solve the problem, technical scheme of the present invention is: the preparation method of this high-purity longifolene by containing weight part be 65% ~ 70% longifolene and weight part be that the mixture of the caryophyllene of 10% ~ 30% puts into reaction vessel, add catalyzer, carry out caryophyllene polyreaction, reaction Heating temperature is 80 ° of C ~ 110 ° C, and the reaction times is 3 ~ 6 hours, filter again, catalyst recovery, underpressure distillation, rectifying the longifolene finished product of 85% ~ 95% content; Described catalyzer is macroporous type acidulous acrylic acid cation exchange resin D113, and the weight ratio of described mixture and described catalyzer is 1:0.05 ~ 0.1.
In caryophyllene polyreaction, caryophyllene generates high boiling dipolymer and polymer, is effectively separated with longifolene when subsequent purification.
In technique scheme, more specifically scheme can be: the weight ratio of described mixture and described catalyzer is 1:0.1.
Owing to have employed technique scheme, the present invention compared with prior art has following beneficial effect:
The preparation method of this high-purity longifolene product, utilize new and effective solid acid catalyst macroporous type acidulous acrylic acid cation exchange resin D113 as catalyzer, carry out the advanced row relax of the elementary finished product of longifolene to turps heavy oil or 65% ~ 70% content, caryophyllene after chemical reaction in elementary finished product is become and differs larger other high boiling substance with longifolene boiling point, and then distill, just can be easy to by underpressure distillation the longifolene finished product steaming more than 85% like this, even reach more than 90% content.
Embodiment
Embodiment one:
The little method for testing of this high-purity longifolene, at a band thermometer, the longifolene primary products entering 100 gram of 65% content in 250 grams of there-necked flasks of agitator and spherical condensation tube are raw material, then add 10 grams of high-performance solid acid D113 and make catalyzer, i.e. macroporous type acidulous acrylic acid cation exchange resin D113, then start agitator and start heating, it is 60 ° of C ° that temperature of reaction controls, sampling analysis caryophyllene content after 3 hours, every sampling in 0.5-1 hour once, until caryophyllene content stops adding after being less than 3% start cooling, be cooled to less than 40 degree, filter successively again, catalyst recovery, the analytical results finally obtaining longifolene crude product is: longifolene content 68.755%, caryophyllene content 2.2%.Longifolene crude product distills, rectifying, and the longifolene intercepting desired content (being greater than 80%, 85% or 90%) according to client's index request is the finished product, and the longifolene product content of this experiment distillation is 89.67%.
The catalyzer filtered out is refunded in 250ml reaction flask, the longifolene primary products entering 100 gram of 65% content are again opened stirring heating and are reacted, it is the same that pot is caught up with in technological operation, repeat above technological operation, catalyzer is made to repeat to carry out 1000 pots of lab scales continuously, the longifolene content of the longifolene crude product reflected remains between 63%-68% substantially, and caryophyllene content remains between 2%-4% substantially, and the activity of catalyzer and effect can keep very well.
Embodiment two:
The extension test of this high-purity longifolene: the longifolene adding 10000 gram of 60% content in the reactor that 20L is with condensation and whipping appts, then add 1000 grams of high-performance solid acid D113 and make catalyzer, i.e. macroporous type acidulous acrylic acid cation exchange resin D113, then start agitator and start heating, it is 90 ° of C ° that temperature of reaction controls, sampling analysis caryophyllene content after 3 hours, every sampling in 0.5-1 hour once, until caryophyllene content stops adding after being less than 3% start cooling, be cooled to less than 40 degree, filter successively again, catalyst recovery, the analytical results finally obtaining longifolene crude product is: longifolene content 62.245%, caryophyllene content 2.3%.Longifolene crude product distills, rectifying, and the longifolene intercepting desired content (being greater than 80%, 85% or 90%) according to client's index request is the finished product, and the longifolene product content of this experiment distillation is 90.17%.
The catalyst recovery filtered out is refunded in 20L reactor, the longifolene primary products entering 10000 gram of 60% content are again opened stirring heating and are reacted, it is the same that pot is caught up with in technological operation, repeat above technological operation, catalyzer is made to repeat to carry out 300 pots continuously, the longifolene content of the longifolene crude product reflected remains between 58%-64% substantially, and caryophyllene content remains between 2%-4% substantially, and the activity of catalyzer and effect can keep very well.
Embodiment three:
The pilot scale of this high-purity longifolene is embodied as: the longifolene 100kg longifolene/pot adding 63% content in pilot scale reactor, then add 10kg high-performance solid acid D113 and make catalyzer, i.e. macroporous type acidulous acrylic acid cation exchange resin D113, then start agitator and start heating, it is 110 ° of C that temperature of reaction controls, sampling analysis caryophyllene content after 3 hours, every sampling in 0.5-1 hour once, until caryophyllene content stops adding after being less than 3% start cooling, be cooled to less than 40 degree, filter successively again, catalyst recovery, the analytical results finally obtaining longifolene crude product is: longifolene content 63.135%, caryophyllene content 2.5%.Longifolene crude product distills, rectifying, and the longifolene intercepting desired content (being greater than 80%, 85% or 90%) according to client's index request is the finished product, and the longifolene product content of this experiment distillation is 88.25%.
The catalyst recovery filtered out is refunded in pilot scale reactor, the longifolene primary products entering 100kg60%-65% content are again opened stirring heating and are reacted, it is the same that pot is caught up with in technological operation, repeat above technological operation, catalyzer is made to repeat to carry out 100 pots continuously, the longifolene content of the longifolene crude product reflected remains between 58%-67% substantially, and caryophyllene content remains between 2%-4% substantially, and the activity of catalyzer and effect can keep very well.
The Testing index of the longifolene so produced is as following table:
According to the data of upper table, can show that the longifolene indices synthesized by present method is up to state standards, and longifolene content brings up to more than 80%.
Claims (2)
1. the preparation method of a high-purity longifolene, it is characterized in that: comprise the following steps: by containing weight part be 65% ~ 70% longifolene and weight part be that the mixture of the caryophyllene of 10% ~ 30% puts into reaction vessel, add catalyzer, carry out caryophyllene polyreaction, reaction Heating temperature is 80 ° of C ~ 110 ° C, and the reaction times is 3 ~ 6 hours, filter again, catalyst recovery, underpressure distillation, rectifying the longifolene finished product of 85% ~ 95% content;
Described catalyzer is macroporous type acidulous acrylic acid cation exchange resin D113, and the weight ratio of described mixture and described catalyzer is 1:0.05 ~ 0.1.
2. the preparation method of high-purity longifolene according to claim 1, is characterized in that: the weight ratio of described mixture and described catalyzer is 1:0.1.
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| CN104193579A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Purification method for longifolene |
| CN105801752B (en) * | 2016-04-05 | 2018-02-13 | 中国林业科学研究院林产化学工业研究所 | A kind of copolymer of β carypohyllenes maleic anhydride and preparation method and application |
| CN106083517A (en) * | 2016-06-28 | 2016-11-09 | 广西梧松林化集团有限公司 | The preparation method of high-purity longifolene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460668A (en) * | 2003-06-02 | 2003-12-10 | 厦门中坤化学有限公司 | Preparation method of isologifolic olefince |
| CN1583690A (en) * | 2004-06-04 | 2005-02-23 | 南京大学 | Preparation of pure longifolene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460668A (en) * | 2003-06-02 | 2003-12-10 | 厦门中坤化学有限公司 | Preparation method of isologifolic olefince |
| CN1583690A (en) * | 2004-06-04 | 2005-02-23 | 南京大学 | Preparation of pure longifolene |
Non-Patent Citations (3)
| Title |
|---|
| 重质松节油催化反应制备高纯度长叶烯的研究;米世伍等;《生物质化学工程》;20060930;第40卷(第5期);第28-30页 * |
| 重质松节油提取高纯度长叶烯的新方法;黄宇平等;《生物质化学工程》;20070131;第41卷(第1期);第37-39页 * |
| 长叶烯异构化制备异长叶烯的研究;周红;《广西化工》;19990630;第28卷(第2期);第17-19,34页 * |
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