CN1171890C - Prepn process and plant of high-purity eudesmin - Google Patents
Prepn process and plant of high-purity eudesmin Download PDFInfo
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- CN1171890C CN1171890C CNB031174140A CN03117414A CN1171890C CN 1171890 C CN1171890 C CN 1171890C CN B031174140 A CNB031174140 A CN B031174140A CN 03117414 A CN03117414 A CN 03117414A CN 1171890 C CN1171890 C CN 1171890C
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Abstract
The present invention discloses a method for preparing high-purity eudesmin, and a device for realizing the method. The whole purification process comprises three steps of crystallization, sweating and melt crystallization which are completed in one identical device, and a final product can be obtained without any post-treatment. Compared with a falling-film crystallization method and other conventional melt crystallization methods, the method of the present invention has the advantages of simple operation, high efficiency and high yield. By only one-time technological process of freezing crystallization, sweating and melt crystallization, a high-purity eudesmin product of which the purity is at least 99.5% is prepared by using eucalyptus oil of which the eudesmin content is at least 70%, and the yield of the eudesmin can reach 33 to 51%.
Description
Technical field
The present invention relates to the separating and purifying method of fine chemical product, the device that more particularly the present invention relates to a kind of preparation method of high purity cineole and realize this method.
Background technology
Cineole is important fine chemical product, is widely used in fields such as Industrial Catalysis, medicine, food, daily necessities; It can be made by terpenoids such as firpenes, also can make with extra care and get from eucalyptus oil.60% thick eucalyptus oil generally can be brought up to its purity about 80%～88% after rectification process.Because thick eucalyptus oil main component is cineole, limonene and right-cymene, its boiling point is respectively 176.0 ℃, and 177.7 ℃ and 177.1 ℃, difference is very little, adopts conventional rectificating method to be difficult to further improve cineole content.
At present, the method from the refining cineole of eucalyptus oil has: supercritical extraction, silica gel column chromatography, chemical reaction method, catalytic rectification process and freeze crystallization.Freeze crystallization does not have the three wastes substantially because simple to operate, can not cause advantage such as corrosion to equipment and becomes main industrial process.Chinese patent (CN1064700A) has been introduced traditional crystallization and purification mode that adopts, with purity is that 80% eucalyptus oil is a raw material-8 ℃～-20 ℃ following freezing and crystallizings 48 hours, behind supercentrifuge separation raffinate, obtain the cineole of purity 99%, yield 21%～42.5%, this method technology is simple, facility investment is little, but this method can't be produced the higher product of purity, and the production cycle is grown, is difficult to according to market situation, produces the product of different purity by the technology adjustment.
Chinese patent (CN1109887A) then adopts the film-falling crystallization technology that is similar to Sulzer-MWB to carry out the purification of eucalyptus oil under-30 ℃, and every through a freezing and crystallizing-sweating-molten brilliant technological process, the purity of eucalyptus oil can improve about 10%.This method so material loss is less, and can be produced the product of different purity owing to be to finish all purifying technique operations in an equipment according to market situation.But make purity more than or equal to 99% product, need prepare purity earlier more than or equal to 90% eucalyptus oil raw material, another shortcoming of this technology is that the single step yield is lower and processing requirement is strict, must be at the temperature control curve condition of the strictness work of finishing drilling, and operation is complicated.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art part, provide a kind of flow process simple, the cycle is shorter, and yield is higher, the preparation method of lower-cost high purity cineole.
Another object of the present invention provides a kind of device that is used to realize preparation method of the present invention.
Purpose of the present invention is achieved by following technical proposals.
Annotate: except as otherwise noted, the percentage ratio that is adopted among the present invention is weight percentage.
The preparation method of high-purity cineole comprises the following steps:
(1) is that 70%～85% one of eucalyptus oil input has stirring, chuck, the top is provided with the tubular interchanger and the bottom is provided with the sedimentation crystallizer of filter plate with purity, and in chuck, feeds circulating frozen liquid;
(2) under agitation, make temperature of charge reduce to-7～-11 ℃, drop into a little cineole crystal seed, after the affirmation crystallization triggers successfully, under the temperature of chuck circulating frozen liquid, kept 1 hour;
(3) the bath temperature is at the uniform velocity lowered the temperature, reduce to-20 ℃～-30 ℃ after 2 hours, and bathing-20 ℃～-30 ℃ maintenances of temperature 2 hours;
(4) stop to stir, the residual liquid in the crystallizer is emitted, and adopt vacuum filtration that raffinate is extracted out;
(5) stopping the hot water that suction filtration and the heat exchange of top part device in crystallizer feed 30 ℃～40 ℃ makes crystallizer internal upper part room temps rise to about 10 ℃～20 ℃; Sweating is carried out in the crystallization of staying in the crystallizer, the part crystal on crystal layer surface is slowly melted, the sweat that forms passes lower floor's crystal and flows out crystallizer naturally, crystal is purified, simultaneously rapidly the circulating frozen liquid temp in the chuck is risen to-8 ℃, and at the uniform velocity heat up, the circulating frozen liquid temp rises to about-2 ℃;
(6) get 1 firm effusive sweat sample every 15 minutes and measure its refractive index, work as η
25 D, adopt the vacuum filtration method that the sweat of remnants is extracted out at≤1.4557 o'clock;
(7) stop suction filtration, the circulating hot water of top heater risen to about 60 ℃, chuck circulating frozen liquid rises to+5 ℃ near, the watery fusion that crystallizer is purified by sweating is flowed out, and promptly gets high-purity cineole product of purity 〉=99.5%.
Be used to realize that device of the present invention is a sedimentation crystallizer, this sedimentation crystallizer comprises shell, agitator, interchanger, and filter screen and filtration card, described agitator, interchanger, filter screen and filtration card all are provided with in the enclosure; The top of described shell is round shape, and outer casing underpart is conical, and described shell is set to chuck, and the bottom of shell chuck is provided with the inlet tube of circulating frozen liquid, and the top of shell chuck is provided with the outlet pipe of circulating frozen liquid; Described agitator and interchanger are arranged on the top of sedimentation crystallizer; Described filtration card is fixedly installed on the bottom of sedimentation crystallizer; Described filter screen covers and filters the card surface.
The present invention compared with prior art has following beneficial effect:
1. what adopt is to be provided with in the tubular sedimentation bed crystallizer of filter plate having stirring, chuck and bottom, under suspended state, allow crystal growth, under action of gravity, constantly be deposited to the bottom then, be piled into loose close appropriateness gradually, help the column crystal layer of the discharge of raffinate and sweat.After freezing and crystallizing finishes, adopt the vacuum filtration mode make raffinate more up hill and dale with crystal separation.
2. in the sweating stage,, make the thermograde on the crystal column formation vertical direction mainly from the upper surface heat supply of crystal column.Because the crystal layer that the present invention forms is thicker, than thick hundred times of shell and tube fusion-crystallization method crystal layer such as Sulzer-MWB, the crystal column top is flowed through downwards in the process of crystal layer by the high-purity crystal of the sweat of thermosetting and partial melting, there is the interior crystallization of long time and crystal layer to contact, can give full play to the effect of sweating, drip washing and recrystallization, thereby guaranteed under the situation of high yield, can improve constantly the crystal purity in the crystal layer.
3. after sweating finishes, adopt vacuum filtration to make sweat emptying as far as possible, at last by the appropriate heat supply at chuck and crystal column top, make the crystal layer after the pure system of sweating melt discharge fully, the high-purity cineole product that promptly makes.
4. whole purification process comprises crystallization, sweating and molten brilliant three steps, all in same equipment, finish, need not any subsequent disposal and just can obtain the finished product, compare with conventional fusion-crystallization methods such as film-falling crystallization methods, this law is simple to operate, and separation efficiency and yield are all higher.Through the technological process of a freezing and crystallizing-sweating-molten material, can be raw material with the eucalyptus oil of cineole content 〉=70% just only, prepare the high purity cineole product of purity 〉=99.5%, the cineole yield reaches 33%～51%.And can only just produce the product of other various purity requirements as required by the one-time process process, the entire operation cycle is only about 10 hours.
5. the apparatus structure advantages of simple of Cai Yonging, easy and simple to handle, facility investment and process cost are lower, and be of many uses, can be common to be fit to other system that the fusion-crystallization method is purified.
Description of drawings
Fig. 1 is a sedimentation structure of mould synoptic diagram of the present invention.
Among Fig. 1: shell 1, interchanger 2, agitator 3, filter screen 4 filters card 5, motor M.
Embodiment
By specific embodiment given below, can further be well understood to the present invention.But they are not limitation of the invention.
Embodiment 1
In crystallizer, drop into eucalyptus oil 2000 grams of purity 80%, and in chuck, feed-11 ℃ of circulating frozen liquid.Under agitation, make temperature of charge reduce to-9 ℃, drop into a little cineole crystal seed, confirm that crystallization triggers successfully after, kept under-11 ℃ of temperature maintenance 1 hour at chuck circulating frozen liquid; Make the speed cooling of bathing 2～3 ℃ of warm on average declines by per 30 minutes then, reduce to-20 ℃ after two hours, and bathing warm-20 ℃ of maintenances 2 hours.Stop to stir, the raffinate in the crystallizer is emitted, and adopt vacuum filtration that raffinate is extracted out as far as possible.Stopping suction filtration and the heat exchange of top part device in crystallizer feeds about 30 ℃～40 ℃ hot water and makes crystallizer internal upper part room temps rise to about 10 ℃～20 ℃, the crystal layer surface is 0 ℃～-2 ℃, sweating is carried out in the crystallization of staying in the crystallizer, the part crystal on crystal layer surface is slowly melted, the sweat that forms passes lower floor's crystal and flows out crystallizer naturally, crystal is purified, simultaneously rapidly the circulating frozen liquid temp in the chuck is risen to-8 ℃, and by the speed continuation intensification that made 1 ℃ of temperature-averaging rising in per 30 minutes, after 3 hours, the circulating frozen liquid temp rises to-2 ℃; Got once firm effusive sweat sample every 15 minutes and measure its refractive index this moment, works as η
25 D, adopt the vacuum filtration method that the sweat of remnants is extracted out as far as possible at≤1.4557 o'clock.Stopping suction filtration, the circulating hot water of top heater is risen to about 60 ℃, chuck circulating frozen liquid rises to+and 5 ℃ of watery fusions that crystallizer is purified by sweating flow out, and promptly get purity is that 99.62% high-purity cineole product 565.3 restrains.
Embodiment 2
In crystallizer, drop into eucalyptus oil 2500 grams of purity 83%, and in chuck, feed-11 ℃ of circulating frozen liquid.Under agitation, make temperature of charge reduce to-9 ℃, drop into a little cineole crystal seed, confirm that crystallization triggers successfully after, kept under-11 ℃ of temperature maintenance 1 hour at chuck circulating frozen liquid; Made the speed of bathing 2.5 ℃～4 ℃ of the average declines of temperature will bathe temperature drop by per 30 minutes then and reduce to-27 ℃, and kept two hours down for-27 ℃ in the bath temperature.Stop to stir, the raffinate in the crystallizer is emitted, and adopt vacuum filtration that raffinate is extracted out as far as possible.Stop suction filtration and the heat exchange of top part device in crystallizer feeds about 30 ℃～40 ℃ hot water, make crystallizer internal upper part room temps rise to about 10 ℃～20 ℃, sweating is carried out in the crystallization that stays in the crystallizer, the part crystal on crystal layer surface is slowly melted, the sweat that forms passes lower floor's crystal and flows out crystallizer naturally, crystal is purified, simultaneously rapidly the circulating frozen liquid temp in the chuck is risen to-8 ℃, and after stopping 1 hour under-8 ℃ of temperature, continue then the speed of 1 ℃ of temperature-averaging rising to be heated up by per 20 minutes, after 2 hours, the circulating frozen liquid temp rises to-2 ℃, got once firm effusive sweat sample every 15 minutes and measure its refractive index this moment, works as η
25 D≤ 1.4557 o'clock; Adopt the vacuum filtration method that the sweat of remnants is extracted out as far as possible.Stop suction filtration, the circulating hot water of top heater is risen to about 60 ℃, chuck circulating frozen liquid rises to+5 ℃, and the watery fusion that crystallizer is purified by sweating is flowed out, and promptly get purity and is high-purity cineole product 1046.8 of 99.7% and restrain.
Embodiment 3～embodiment 7
Charging capacity is 2500 grams, and material purity is thrown brilliant temperature, the operation of crystallization final temperature according to the form below, and other process is all with embodiment 2.
| The embodiment title | Material purity (%) | Throw brilliant temperature (℃) | The whole temperature of crystallization (℃) | Product content (%) | Product yield (%) |
| Embodiment 3 | 70.2 | -11 | -26 | 99.5 | 33.6 |
| Embodiment 4 | 71.5 | -11 | -30 | 99.5 | 35.3 |
| Embodiment 5 | 74.6 | -10 | -26 | 99.6 | 36.5 |
| Embodiment 6 | 81.3 | -9 | -23 | 99.8 | 40.3 |
| Embodiment 7 | 84.5 | -7 | -23 | 99.8 | 46.6 |
Claims (3)
1. the preparation method of a high-purity cineole, this method comprises the following steps:
(1) is that 70%～85% one of eucalyptus oil input has stirring, chuck, the top is provided with the tubular interchanger and the bottom is provided with the sedimentation crystallizer of filter plate with purity, and in chuck, feeds circulating frozen liquid;
(2) under agitation, make temperature of charge reduce to-7～-11 ℃, drop into a little cineole crystal seed, after the affirmation crystallization triggers successfully, under the temperature of chuck circulating frozen liquid, kept 1 hour;
(3) the bath temperature is at the uniform velocity lowered the temperature, reduce to-20 ℃～-30 ℃ after 2 hours, and bathing-20 ℃～-30 ℃ maintenances of temperature 2 hours;
(4) stop to stir, the residual liquid in the crystallizer is emitted, and adopt vacuum filtration that raffinate is extracted out;
(5) stopping the hot water that suction filtration and the heat exchange of top part device in crystallizer feed 30 ℃～40 ℃ makes crystallizer internal upper part room temps rise to about 10 ℃～20 ℃; Sweating is carried out in the crystallization of staying in the crystallizer, the part crystal on crystal layer surface is slowly melted, the sweat that forms passes lower floor's crystal and flows out crystallizer naturally, crystal is purified, simultaneously rapidly the circulating frozen liquid temp in the chuck is risen to-8 ℃, and at the uniform velocity heat up, the circulating frozen liquid temp rises to about-2 ℃;
(6) get 1 firm effusive sweat sample every 15 minutes and measure its refractive index, work as η
25 D, adopt the vacuum filtration method that the sweat of remnants is extracted out at≤1.4557 o'clock;
(7) stop suction filtration, the circulating hot water of top heater risen to about 60 ℃, chuck circulating frozen liquid rises to+5 ℃ near, the watery fusion that crystallizer is purified by sweating is flowed out, and promptly gets high-purity cineole product of purity 〉=99.5%.
2. device that is used to prepare high-purity cineole, this device is one and comprises shell, agitator, interchanger, the sedimentation crystallizer of filter screen and filtration card, it is characterized in that described agitator, interchanger, filter screen and filtration card all are arranged in the same shell, and described shell is set to chuck, the bottom of shell chuck is provided with the inlet tube of circulating frozen liquid, and the top of shell chuck is provided with the outlet pipe of circulating frozen liquid.
3. device according to claim 2, the top of its described shell are round shape, and outer casing underpart is conical, and described agitator and interchanger are arranged on the top of sedimentation crystallizer; Described filtration card is fixedly installed on the bottom of sedimentation crystallizer; Described filter screen covers and filters the card surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031174140A CN1171890C (en) | 2003-03-05 | 2003-03-05 | Prepn process and plant of high-purity eudesmin |
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| CNB031174140A CN1171890C (en) | 2003-03-05 | 2003-03-05 | Prepn process and plant of high-purity eudesmin |
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| CN1171890C true CN1171890C (en) | 2004-10-20 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899361B (en) * | 2010-08-04 | 2012-07-11 | 福建森美达生物科技有限公司 | Single-tower continuous rectification method of eucalyptus oil |
| CN103752031B (en) * | 2014-02-08 | 2015-10-14 | 山东科信生物化学有限公司 | A kind of crystallization filter plant that can overturn |
| CN103755661B (en) * | 2014-02-08 | 2016-09-21 | 山东省农药科学研究院 | A kind of separation and refining method of 2-chloro-5-chloromethyl thiazole |
| CN104211710B (en) * | 2014-09-28 | 2016-08-24 | 福建森美达生物科技有限公司 | A kind of freezing and crystallizing extracting method of 1,8-cineole |
| CN104761566B (en) * | 2015-03-25 | 2017-03-01 | 昆明理工大学 | A kind of method of low concentration eucalyptus oil crystallization and purification |
| CN106554360A (en) * | 2016-11-21 | 2017-04-05 | 四川省林业科学研究院 | A kind of method of 1,8 Cineoles in purification yusho oil |
| CN109293671A (en) * | 2018-09-04 | 2019-02-01 | 中粮德信行健康产业有限公司 | A kind of purification process of Cineole |
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