CN1109887A

CN1109887A - Process for preparing high-purity natural eudesmin

Info

Publication number: CN1109887A
Application number: CN 94119064
Authority: CN
Inventors: 李士雨; 王静康; 薛履中; 王玉德; 秦文军
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 1994-12-28
Filing date: 1994-12-28
Publication date: 1995-10-11

Abstract

A fusion crystalline process is used to prepare high-purity natural eudesmin from natural eucalyptus oil. The eucalyptus oil with 60% purity goes through freeze-crystalline, evporation and fusion in crystallizer with jacket and material-liquid distributor for increasing purity by 10% in each step. After one technological process, the purity may be increased from 90% to 99%.

Description

Process for preparing high-purity natural eudesmin

The invention belongs to the separating and purifying method of chemical industry fine chemical product.

By foline is important fine chemical product, and it is widely used in fields such as Industrial Catalysis, medicine, food, daily necessities; It can make by terpin is synthetic, also can make from eucalyptus oil.

In the method that adopts refining cineole from eucalyptus oil, mainly contain following several method:

1, supercritical extraction, thermodynamic study shows that the separating power of this method is very low;

2, silica gel column chromatography, it can make the high purity cineole, but treatment capacity is little, is not suitable for scale operation;

3, chemical reaction method makes eucalyptus oil and HCl, HBr, H ₃PO ₄, materials such as Resorcinol react under certain condition and can generate the crystallinity affixture, and reheat hydrolysis crystallization can be made into high-purity cineole through rectification process;

4, catalytic rectification process uses nickel catalyzator in rectifying, and bubbling air makes some oxidation of impurities, also can make cineole obtain enrichment, but can not get high-purity cineole;

5, the crystallizing process under low temperature, because the special crystallographic property of cineole, the crystallization processes process of having delivered often can not get high-purity cineole, only make 85% cineole as people such as Nigharedz, people such as Proenca da Cuuda Antonia are raw material with 69.5% eucalyptus oil, through a step crystallization, can make purity and be 92% cineole under-30 ℃, its cycle is 17 hours, the employing raffinate refluxes, and behind vacuum filtration, yield is 48%; Use again 90% ethanol under same temperature (30 ℃) wash crystallization repeatedly, can make cineole purity reach 96%, again with 96% cineole with after 90% ethanol mixed with 1: 1, still-30 ℃ of crystallizations, can make 98.3% cineole product, this crystallisation process yield is 40%.

Be not difficult to find out that from said process for current technology, it is feasible making high-purity cineole by chemical reaction method, yield is also higher, but technological process exists and needs secondary separation, the flow process more complicated; Technological process has certain corrodibility, has increased the erosion-resisting requirement of equipment; Also there is harmful material in technological process, and is not thorough during separation, also can influence the quality of cineole, so the development of chemical reaction method is subjected to certain limitation.Though there is not above-mentioned drawback in the crystallizing process under low temperature, then difficulty is bigger to make the high purity cineole, needs to purify repeatedly preparation, and it is long to have formed the production cycle, and the big defective that yield is low and cost is higher is promoted for industry and brought difficulty.

The objective of the invention is in order to overcome the big defective that current technology exists and to try hard to realize that a kind of flow process is simple, cycle is shorter, yield is higher, the lower-cost novel process that makes the high purity cineole, just a kind of natural eucalyptus oil that utilizes adopts the fusion-crystallization legal system to be equipped with the novel process of high-purity natural cineole.

The preparation method of the high-purity natural eudesmin that the employing fusion-crystallization method that the present invention proposes realizes is under strict temperature control condition, utilize jacketed type also to have single tube (or tubulation) crystallizer of feed liquid sparger, by crystallization-sweating-melting process process, make high-purity natural eudesmin.

The preparation method of the high-purity natural eudesmin that the present invention proposes, its technical process as shown in Figure 1, among the figure:

1 ,-sweat jar 2 ,-product jar 3 ,-head tank

4 ,-crystallizer 5 ,-recycle pump 6 ,-feed liquid sparger

7 ,-circulation tube

4 shown crystallizers are the single tube crystallizer with chuck of taking the lead to overlap among the figure, its top is a material storing room (headgear), material storing room bottom and single tube junction are connected with A-A place among the feed liquid sparger 6(figure in uniform 6～12 holes, as shown in Figure 2), the straight tube that extends upward at its middle part is the feed liquid control tube, prevents that feed liquid from flowing directly into interior pipe, and the following straight-tube portion of feed liquid sparger is the crystallizer main body, its below links to each other with circulation tube 7, and not crystallization feed liquid is returned head tank.

Technological process of the present invention is sent into material storing room with stock liquid by recycle pump 5 for elder generation and is flowed into the interior pipe of crystallizer 4 through sparger, simultaneously, then feed refrigerant in the jacket pipe, after being cooled to certain temperature, feed liquid begins at interior duct ligation crystalline substance, be cooled to about-30 ℃ through 20 minutes approximately, when the brilliant material of interior duct ligation reaches certain thickness, stop charging and kept constant temperature 20～60 minutes, refrigerant temperature then gradually raises, mould temperature rises to-20 ℃ through about 10 minutes approximately, so that discharging, the impurity in the crystallization delivers to sweat jar 1 from crystal layer, and keep constant temperature about 10 minutes, continuing to heat up made temperature rise to-5 ℃ in 15 minutes again, kept constant temperature about 35 minutes again, separate the purpose of purifying to reach, be warming up to 0～5 ℃ of molten material at last again, obtain cineole finished product or intermediates and deliver to side by side in the product jar 2, so far then finished the one-time process process.The temperature control process of crystallization-sweating-melt whole process as shown in Figure 3.For initial purity is eucalyptus oil feed liquid more than 60%, every through the one-time process treating processes, and its purity can improve 10% approximately, is 90% eucalyptus oil feed liquid for purity, and through the one-time process process, cineole purity can reach 99%; Total recovery can reach 60～80%.

Be example now, further narrate the process of process implementing of the present invention with the single tube crystallizer:

Embodiment: be 90% eucalyptus oil feed liquid with purity, storage is gone in the head tank, start the recycle pump and the refrigerant recycle system, mould temperature is reduced to below-5 ℃ gradually, material then forms crystallization at inside pipe wall gradually, after reaching certain thickness to crystallizing layer, close recycle pump, mould temperature then continues to reduce to about-30 ℃, kept constant temperature 20 minutes, improve the temperature of refrigerant then with the temperature speed of 1 ℃ of per minute, impurity in the crystal layer is discharged with liquid form through sweating deliver to the sweat jar, be warming up to about-20 ℃ and kept constant temperature 10 minutes, continue to heat up again and reached-5 ℃ and kept constant temperature 35 minutes in 15 minutes, be beneficial to separate to purify, melt during temperature rise to 0～5 ℃ obtains purity and is 99% cineole product.

Claims

1, a kind of preparation method who utilizes natural eucalyptus oil to adopt the high-purity natural eudesmin of fusion-crystallization method, it is characterized in that under strict temperature control curve condition having to finish in chuck and the single tube feed liquid sparger (or tubulation) crystallizer one and separate purification process; With purity is that stock liquid more than 60% is sent into the material storing room by the crystallizer top of refrigerant temperature control, via managing crystallization gradually in the feed liquid sparger inflow crystallizer, reduce to-30 ℃ and kept constant temperature 20 minutes through 20 minutes temperature, treat to stop charging after crystal layer reaches certain thickness, crystallization this moment and temperature-fall period carry out simultaneously, begin behind the constant temperature to heat up, rose to-20 ℃ through 10 minutes, the impurity that have in the crystal layer this moment is discharged with liquid form through sweating, 10 minutes follow-up temperature of continuing rising of constant temperature, through extremely-5 ℃ of temperature rises in 15 minutes, kept constant temperature 35 minutes, the impurity in the crystal layer continues to discharge with liquid form at this moment, separates the purpose of purifying to reach, then continue to be warming up to 0～5 ℃ behind the constant temperature, it is 99% cineole product that the beginning melt obtains intermediates or purity, and every through the one-time process process, the purity of eucalyptus oil can improve 10%, with purity is that 90% eucalyptus oil is a raw material, can obtain purity and be 99% product.