CN103449954A

CN103449954A - Preparation method of high-purity longifolene

Info

Publication number: CN103449954A
Application number: CN2013103779272A
Authority: CN
Inventors: 陈键泉; 陈伟强; 孔仕才; 车乾池; 黄宇平; 杨振洲; 梁利诚; 苏炳连; 李战
Original assignee: WUZHOU SONGHUA AROMATIC CHEMICALS CO Ltd
Current assignee: WUZHOU SONGHUA AROMATIC CHEMICALS CO Ltd
Priority date: 2013-08-27
Filing date: 2013-08-27
Publication date: 2013-12-18
Anticipated expiration: 2033-08-27
Also published as: CN103449954B

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

The preparation method of high purity longifolene

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 to realize by underpressure distillation, and underpressure distillation is difficult to be purified to 80% above longifolene, reason is the composition that contains a kind of caryophyllene in heavy oil, the boiling point of caryophyllene and physical property are very approaching with longifolene, 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 of processing, can only distill the longifolene that obtains 65%～70% content.Meeting 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, to solve existing longifolene production, obtain the not high problem of longifolene product content.

In order to address the above problem, technical scheme of the present invention is: the mixture that the preparation method of this high purity longifolene will contain the caryophyllene that longifolene that weight part is 65%～70% and weight part are 10%～30% is put into reaction vessel, add catalyzer, carry out the caryophyllene polyreaction, the reaction Heating temperature is 80 ° of C～110 ° C, and the reaction times is 3～6 hours, filtered again, catalyst recovery, underpressure distillation, rectifying gets final product to obtain 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 the caryophyllene polyreaction, caryophyllene generates high boiling dipolymer and polymer, when subsequent purification, effectively with longifolene, separates.

In technique scheme, more specifically scheme can be: the weight ratio of described mixture and described catalyzer is 1:0.1.

Owing to having adopted 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 elementary finished product of longifolene of turps heavy oil or 65%～70% content is first processed, caryophyllene after chemical reaction in elementary finished product is become with the longifolene boiling point and differs larger other high boiling substance, and then distilled, just can be easy to steam the longifolene finished product more than 85% by underpressure distillation like this, even reach 90% above content.

Embodiment

Embodiment mono-:

The little method for testing of this high purity longifolene, at a band thermometer, the longifolene primary products of advancing 100 gram 65% content in 250 gram there-necked flasks of agitator and spherical condensation tube are raw material, then add 10 gram high-performance solid acid D113 to make catalyzer, be macroporous type acidulous acrylic acid cation exchange resin D113, then start agitator and start heating, it is 60 ° of C ° that temperature of reaction is controlled, sampling analysis caryophyllene content after 3 hours, every sampling in 0.5-1 hour once, until stopping adding after being less than 3%, caryophyllene content starts to lower the temperature, be cooled to below 40 degree, filtered successively again, catalyst recovery, the analytical results that finally obtains the longifolene crude product is: longifolene content 68.755%, caryophyllene content 2.2%.The longifolene crude product is distilled, and rectifying is the finished product according to the longifolene of client's index request intercepting desired content (being greater than 80%, 85% or 90%), and the longifolene product content of this experiment distillation is 89.67%.

The catalyzer filtered out is refunded in the 250ml reaction flask, the longifolene primary products of advancing again 100 gram 65% content are opened stirring heating and are reacted, technological operation is caught up with pot equally, repeat above technological operation, make catalyzer repeat to carry out continuously 1000 pots of lab scales, 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 finely.

Embodiment bis-:

The extension test of this high purity longifolene: the longifolene that adds 10000 gram 60% content in the reactor at 20L with condensation and whipping appts, then add 1000 gram high-performance solid acid D113 to make catalyzer, be macroporous type acidulous acrylic acid cation exchange resin D113, then start agitator and start heating, it is 90 ° of C ° that temperature of reaction is controlled, sampling analysis caryophyllene content after 3 hours, every sampling in 0.5-1 hour once, until stopping adding after being less than 3%, caryophyllene content starts to lower the temperature, be cooled to below 40 degree, filtered successively again, catalyst recovery, the analytical results that finally obtains the longifolene crude product is: longifolene content 62.245%, caryophyllene content 2.3%.The longifolene crude product is distilled, and rectifying is the finished product according to the longifolene of client's index request intercepting desired content (being greater than 80%, 85% or 90%), and the longifolene product content of this experiment distillation is 90.17%.

The catalyst recovery filtered out is refunded in the 20L reactor, the longifolene primary products of advancing again 10000 gram 60% content are opened stirring heating and are reacted, technological operation is caught up with pot equally, repeat above technological operation, make catalyzer repeat to carry out continuously 300 pots, 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 finely.

Embodiment tri-:

The pilot scale of this high purity longifolene is embodied as: add the longifolene 100kg longifolene of 63% content/pot in the pilot scale reactor, then add 10kg high-performance solid acid D113 to make catalyzer, be macroporous type acidulous acrylic acid cation exchange resin D113, then start agitator and start heating, it is 110 ° of C that temperature of reaction is controlled, sampling analysis caryophyllene content after 3 hours, every sampling in 0.5-1 hour once, until stopping adding after being less than 3%, caryophyllene content starts to lower the temperature, be cooled to below 40 degree, filtered successively again, catalyst recovery, the analytical results that finally obtains the longifolene crude product is: longifolene content 63.135%, caryophyllene content 2.5%.The longifolene crude product is distilled, and rectifying is the finished product according to the longifolene of client's index request intercepting desired content (being greater than 80%, 85% or 90%), and the longifolene product content of this experiment distillation is 88.25%.

The catalyst recovery filtered out is refunded in the pilot scale reactor, the longifolene primary products of advancing again 100kg60%-65% content are opened stirring heating and are reacted, technological operation is caught up with pot equally, repeat above technological operation, make catalyzer repeat to carry out continuously 100 pots, 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 finely.

The detection index of the longifolene of so producing is as following table:

According to the data of upper table, can show that the longifolene indices synthetic by present method is up to state standards, and longifolene content has been brought up to more than 80%.

Claims

1. the preparation method of a high purity longifolene, it is characterized in that: comprise the following steps: the mixture of the caryophyllene that the longifolene that will to contain weight part be 65%～70% and weight part are 10%～30% is put into reaction vessel, add catalyzer, carry out the caryophyllene polyreaction, the reaction Heating temperature is 80 ° of C～110 ° C, and the reaction times is 3～6 hours, filtered again, catalyst recovery, underpressure distillation, rectifying gets final product to obtain 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, it is characterized in that: the weight ratio of described mixture and described catalyzer is 1:0.1.