CN85101597A - From turps, separate α-and beta-pinene with additive - Google Patents

Abstract

From turps, separate α-and beta-pinene with additive.The invention belongs to method, the extraordinary distillation technique of separation and Extraction α-Pai Xi and beta-pinene from turps with additive.Additive is added to by a certain percentage in the turps of purification, carry out fractionation with a separation column with 32 theoretical plate numbers, overhead product is at normal temperatures and pressures through the water extracting and purifying, can get purity and reach 99% α-Pai Xi, 85% above beta-pinene, the one way extraction yield is more than 90%, and about the existing common fractionating process of rate ratio in the unit time doubled, additive can recycling use.

Description

From turps, separate α-and beta-pinene with additive

The invention belongs to extraordinary Zheng Evaporated method, separation and Extraction high-quality, high yield α-Pai Xi and beta-pinene from turps with additive.

Essential oil resource-turps output the most large in China's natural product occupies first place in the world.According to the study, contain α-Pai Xi (65～86%), beta-pinene (3～36%) and longifolene, myrcene, β-caryophyllene He 30 various ingredients such as limonene in the turps.Wherein α-Pai Xi and beta-pinene are the important source material of making spices, medicine and Minute Organic Synthesis industry, as being raw material with α-Pai Xi, beta-pinene, can synthesize nearly 100 kinds of spices and artificial camphor, borneol, vitamin-E and terpine resin etc.

Separation and Extraction α-Pai Xi and beta-pinene from turps, external employed industrial method are to adopt traditional De Jing Evaporated method.With the state-of-the-art Britain of equipment and technology BBA(Bush Boake Allen) the Glidden company (J.Am.Chem.Soc.76 2669～71(1954)) of company and the U.S. is example, all be to adopt more than 100 layers theoretical tray (being equivalent to the high) De of tens floors Jing Evaporated tower directly separates, control high like this De Jing Evaporated tower, complex facilities such as modern computer, senior self-service instrument must be equipped with, the normal operation of Jing Evaporated process could be guaranteed.Though this traditional De Jing Evaporated method can obtain highly purified product, exists the equipment complexity, investment and technical supervision expense are bigger, and energy consumption is big, the not high shortcoming of output in the unit time.

Domestic currently used method remains traditional De Jing Evaporated method, and 55～67 layers of the theoretical trays of Qi Jing Evaporated tower need carry out repetition Zheng Evaporated operation, separating effect is, the beta-pinene extraction yield only reaches 25～65%, and product purity is about 85%, energy consumption is big, yield poorly, and raw material availability is low.

In addition, in the method that some research units adopt, use chromatography in addition both at home and abroad.The characteristics of this method are isolating product purity height, but being only applicable to the laboratory, this method prepares in a small amount, and the cost of equipment costliness, be not suitable for industrial mass production.

The invention reside in provides a kind of easy, and equipment and technical qualification are less demanding and can obtain the separating and extracting method of high-quality, high yield effect.This method is that this ideal solution system of turps is added a kind of additive, and making system transition is the enough big nonideal solution system of a deviation.By research to the vapour-liquid equilibrium rule and the liquid-liquid equilibrium rule of this nonideal solution, and by research to this system molecular property and molecular aggregates state behavior, finding out the activity quotient that can make each component changes and to reach each component and be easy to isolating effective additive, this additive is added in the turps that purifying treatment crosses, with the Hang Fen Evaporated of the not high De Fen of theoretical tower utmost point number of plies Evaporated tower Jin, then Evaporated is gone out thing and carry out the water extraction at normal temperatures and pressures, just can from turps, separate expeditiously and obtain the very high α-Pai Xi of purity, beta-pinene and other components, each compound in the mixed system that also can be used to separate petrochemical complex obtains through platinum reforming three kinds of xylene isomers and ethylbenzene that uses the same method.

Specific practice of the present invention is: with crude turpentine by volume, water: NaOH(about 0.2%) aqueous solution: oil=1: 1: 4, at normal temperature, carry out purifying treatment under the normal pressure, wash with water again to being neutral, turps after the purification is oil by volume: additive=9: 1 adding additives, has 30-50 theoretical plate number De Fen Evaporated tower-" α-Pai Xi Fen Evaporated tower " Hang Fen Evaporated of Jin with one then, working pressure is controlled to be 150-360mmHg in its tower, tower still temperature is controlled to be 110-140 ℃, tower top temperature is controlled to be in the 90-110 ℃ of Zai Fen Evaporated process, and the collection of product is determined and controlled to the refractive index that goes out the oil in the thing with Jian Ce Evaporated.Evaporated goes out thing and is divided into two liquid phase layers at normal temperatures, contains additive about 99.8% in the heavy phase layer (lower floor); Contain in the light layer (upper strata) mutually additive less than 0.01% all the other be that purity is 98～99.5% α-Pai Xi.Two liquid phase layers of weight that Evaporated is gone out thing divide earlier and remove the heavy phase layer (main component is an additive, recyclable recycling), light layer mutually is then oily by volume: water=4: 1, carry out the water extraction at normal temperatures and pressures to remove additive, extraction phase is that heavy phase is the aqueous solution that contains trace mineral supplement and a small amount of oil (recyclable recycle or discard), and gently be exactly mutually purity be 98～99.5% α-Pai Xi product.

" α-Pai Xi Fen Evaporated tower " surplus liquid of tower still had 30-50 theoretical tray De Fen Evaporated tower-" beta-pinene Fen Evaporated tower " Hang Fen Evaporated of Jin with another, tower inner control pressure is: 150～360mmHg, tower still temperature is controlled to be 120～140 ℃, tower top temperature is controlled to be 110～120 ℃, receives the same way with the refractive index of measuring oil of determining that collection Evaporated goes out thing.Evaporated goes out the thing direct layering, the heavy phase layer contains additive about 99.8%, can send " α-Pai Xi Fen Evaporated tower " back to recycles, light layer mutually is water by volume: oil=1: 4 is depressed at normal temperature and is extracted, extraction liquid (heavy phase) only contains trace mineral supplement, recyclable utilization or discard promptly is that purity is 88～95% beta-pinene product mutually gently.Above-mentioned " beta-pinene Fen Evaporated tower " also can close And with " α-Pai Xi Fen Evaporated tower " is same tower, the same only needs 30-50 theoretical trays, by the control felicity condition, steams α-Pai Xi earlier, after steam beta-pinene again.

" beta-pinene Fen Evaporated tower " tower bottoms contains longifolene, myrcene and other multiple components, and the also available above-mentioned same method of these blending ingredients by adding additive and the suitable De Fen Evaporated condition of control, is separated them one by one.

Aspect petrochemical complex, obtain after the platinum reforming right-dimethylbenzene ,-mix products of dimethylbenzene, ortho-xylene and ethylbenzene, its separation also can be used aforesaid method, promptly adds additive, controls the condition of Fen Evaporated well, also each isomer separation can be come.

Additive used in the present invention once carried out extensive experimentation, as once using various types of compounds such as various alcohols, ester class, ethers, ketone, amine, and compound of the same type had been made the campaign of homologue.Find that wherein effect has ethylene glycol, ethanamide, methyl lactate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether etc. preferably, wherein the best ethylene glycol of effect, ethanamide the two all be extremely common industrial chemicals, low price, be easy to get, and almost all recycling uses, these two kinds of additives all have stable performance, high blast, the low toxin of being difficult for of flash-point.

The inventive method relatively sees Table 1 with the separation and Extraction result of the method for present domestic and international employed Chuan Tong Fen Evaporated.

As seen the inventive method relatively has following advantage with present domestic and international employed method:

The inventive method uses De Jing Evaporated tower only to need 30-50 theoretical plate number, theoretical plate number well below present domestic and international employed Jing Evaporated tower, the purity height of the product that the purity of product obtains than present domestic use Chuan Tong Fen Evaporated method, and suitable with external state-of-the-art company product.From refluxing recently, the output of the present domestic and international method that adopts of rate ratio doubles approximately in the inventive method unit time.In addition, the present invention to beta-pinene content requirement in the crude turpentine is minimum can 5%, be applicable to the terebinthine separation that are produced from China each department fully.

Claims (10)

1, a kind ofly washes, washes later method with extraordinary distillation and extraction separation and Extraction α-Pai Xi and beta-pinene from turps through diluted alkaline, it is characterized in that when distillation, adding a kind of additive, with " α-Pai Xi separation column " rectifying, get " beta-pinene separation column " rectifying of " α-Pai Xi separation column " tower bottoms more earlier.

2,, it is characterized in that institute's doping can be ethylene glycol, ethanamide, methyl lactate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether according to the described method of claim 1.

3,, it is characterized in that institute's doping and the volume ratio that purifies turps are 1: 9 according to claim 1,2 described methods.

4,, it is characterized in that used Jing Evaporated tower has 30-50 theoretical tray according to the described method of claim 1.

5, according to the described method of claim 1, it is characterized in that " α-Pai Xi Fen Evaporated tower " control condition is: the tower internal pressure is 150～360mmHg, 110～140 ℃ of tower still temperature, 90～110 ℃ of tower top temperatures.

6, according to the described method of claim 1, it is characterized in that " beta-pinene Fen Evaporated tower " control condition is: tower internal pressure 150～360mmHg, 120～140 ℃ of tower still temperature, tower top temperature are 110～120 ℃.

7,, it is characterized in that Jiang the extraction of the light layer mutually of Evaporated fluid water, to remove trace mineral supplement according to the described method of claim 1.

8,, it is characterized in that extraction agent water is volume ratio 1: 4 with the light ratio of layer mutually according to the described method of claim 7.

9,, it is characterized in that can be used to separate other components in the purification turps according to claim 1,2 described methods.

10,, it is characterized in that can be used to separate each one-component in the mixed system of platinum reforming in the petrochemical complex obtains three kinds of xylene isomers and ethylbenzene according to claim 1,2 described methods.