CN1973940A - Process of extracting and separating effective components from plant continuously - Google Patents
Process of extracting and separating effective components from plant continuously Download PDFInfo
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- CN1973940A CN1973940A CN 200610097571 CN200610097571A CN1973940A CN 1973940 A CN1973940 A CN 1973940A CN 200610097571 CN200610097571 CN 200610097571 CN 200610097571 A CN200610097571 A CN 200610097571A CN 1973940 A CN1973940 A CN 1973940A
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Abstract
The process of extracting and separating effective components from plant material continuously is different essentially from traditional solvent extraction process in that solvent with low solubility on effective components and high selectivity on impurity is selected and that continuous extraction with flowing solvent and continuous selective transfer of the effective components with one other solvent phase or regeneration circulating extraction and separation of solvent is adopted. The present invention reach simultaneous extraction and separation by means of the continuous circular operation mode, and has greatly reduced solvent return quantity, reduced evaporation recovering and regenerating of solvent, low power consumption and solvent consumption and raised safety.
Description
Technical field
The present invention relates to the method for effective component extracting from natural plants, the method for active ingredient in especially a kind of continuous extraction separating plant.
Background technology
The plant extracts industry is to answer international market demand and an emerging industry producing, and its technology and quality control still are among the continuous development.For making Chinese medicine can obtain better to inherit and development, promote that Chinese medicine enters the international market, obtain international endorsement, the domestic notion that has also progressively formed Chinese medical extract, and started modernization of Chinese medicine engineering, its objective is make tcm product from research and develop in the quality control near or surpass external natural products.
Plant extracts is the active ingredient of separating from plant.Effective component extracting generally all adopts solvent method from plant.This method is to utilize the dissolving of solvent to active ingredient, and active ingredient is separated from plant.Its process comprises utilizes solvent from plant the active ingredient dissolving to be diffused out, and obtains the process of extract and obtains crude extract by reclaiming after solvent concentrates by Separation of Solid and Liquid.This moment, active constituent content was also low owing to crude extract ingredient complexity, also needed the purge process of a step or multistep usually.
Yet in order to achieve the above object, the typical way of tradition was in the past: utilize the similar principle that mixes, select greatly to extract (active ingredient) solubility, simultaneously the as far as possible little solvent of the solubility of impurity is extracted.The benefit of this way is fast as far as possible active ingredient is separated from plant, and the quantity of solvent of using is less, but the critical defect of its existence is: extracted in a large number simultaneously with strong, the weak close impurity of active ingredient polarity, certainly will increase the separating difficulty of later process like this, finally cause extraction effect poor.Its reason is: the first, because active ingredient and strong, the weak close impurity of its polarity exist simultaneously, remove these impurity and need pass through separating for several times, and separating difficulty is big.Second, because effective components in plants content is very low usually, plant itself has the big characteristic of proportion small size again, it is just big to make solvent can soak the quantity of solvent that medicinal material needs fully, the medicinal material adsorption solvent needs repeatedly to extract could be near extracting fully, the accumulative total solvent load usually needs the quantity of solvent more than at least ten times, causes that solvent use amount yield is big, loss is high, energy consumption is high, labour intensity is big.The 3rd, being heated for a long time causes the destruction of active ingredient, and yield descends, and impurity component destroys and causes separation difficulty simultaneously.Exist just because of the impurity of strong, weak two-phase polarity is a large amount of simultaneously, often need through a few step purifying, sedimentation, extraction, post separation etc., solvent load is big, operation is loaded down with trivial details, active ingredient loss height, labour intensity are big, strong to people's operation dependency, easily causes controlling the increase of failure cost.
Cause the principal element of above problem to be that the extract industry is to grow up on the basis of traditional Chinese patent drug production, still continue to use tradition on the thinking the big solvent selection mode of active ingredient solubility is carried out crude separation, and then consider other means of purification, thereby restricted the technological progress of extract.
Summary of the invention
The present invention is from the angle of reverse thinking, to select exchanging for the dopant type selectivity to the solvent a little less than the active ingredient dissolubility is by force core, the method of active ingredient in a kind of continuous extraction separating plant is proposed, its objective is means by successively separating strong polar impurity and low pole impurity, improve effective component extracting technical merit and quality from natural plants, overcome the deficiencies in the prior art.
For achieving the above object, first technical scheme that the present invention adopts is: the method for active ingredient in a kind of continuous extraction separating plant comprises following content:
(1), diacolation extracts
With the plant that contains active ingredient is raw material, selection to the active ingredient dissolubility a little less than, and to respect to the strong solvent of the strong impurity of active ingredient polarity or the impurity dissolubility a little less than the polarity for extracting solvent, extract continuously in the mode of solvent continuous-flow by continuous diacolation method and to contain active ingredient and with respect to the strong impurity of active ingredient polarity or the extract (and opposite polarity impurity is not suggested) of the impurity a little less than the polarity as far as possible; Described extraction solvent to the complete dissolubility of effective components in plants in following scope: dissolve active ingredient needs 〉=10 liter in the per kilogram plant fully, the solvent load of＜35 liters of scopes;
(2), extraction is shifted
With the extract is object, select on the contrary with the extraction solvent polarity, and immiscible solvent is extractant, by the mode of continuous extration method with solvent continuous-flow, active ingredient in the extract transferred to obtain extract in the extractant, and impurity is retained in and extracts in the solvent;
(3), circulation combination continuously
The extraction solvent that reclaims from extraction or regenerate drops into diacolation again and extracts, and constitutes continuous extraction circulation with this; Purified or/and concentrated coarse crystallization or the product of obtaining of extract or/and reclaim concentrating or the extractant of regeneration drops into the extraction transfer again, constitutes continuous extraction cycle with this from purifying.
For achieving the above object, second technical scheme that the present invention adopts is: the method for active ingredient in a kind of continuous extraction separating plant comprises following content:
(1), diacolation extracts
With the plant that contains active ingredient is raw material, selection to the active ingredient dissolubility a little less than, and to respect to the strong solvent of the strong impurity of active ingredient polarity or the impurity dissolubility a little less than the polarity for extracting solvent, extract continuously in the mode of solvent continuous-flow by continuous diacolation method and to contain active ingredient and with respect to the strong impurity of active ingredient polarity or the extract of the impurity a little less than the polarity; Described extraction solvent to the complete dissolubility of effective components in plants in following scope: dissolve active ingredient needs 〉=10 liter in the per kilogram plant fully, the solvent load of＜35 liters of scopes;
(2), absorption is shifted
With the extract is object, and selected adsorbent adopts column chromatography method with extract continuous-flow mode selective absorption active ingredient, and the desorbed solution that the parsing adsorbent obtains is directly as product or again through the concentrated coarse crystallization that obtains; Impurity is retained in and extracts in the solvent in the adsorption process, and the extraction solvent of recovery or regeneration drops into diacolation again and extracts, and constitutes continuous extraction circulation with this.
Related content in the technique scheme is explained as follows:
1, in above-mentioned first scheme, described purifying is to be object with the extract, selected adsorbent adopts column chromatography method with extract continuous-flow mode selective absorption active ingredient, and the desorbed solution that the parsing adsorbent obtains is directly as product or again through the concentrated coarse crystallization that obtains; Impurity is retained in the extractant in the adsorption process, and the regeneration extractant is used for cycling extraction.
2, in above-mentioned first and second schemes, described extraction solvent to the complete dissolubility of effective components in plants in following better scope: dissolve active ingredient needs 〉=12 liter in the per kilogram plant fully, the solvent load of≤25 liters of scopes, optimum range: dissolve active ingredient needs 〉=15 liter in the per kilogram plant fully, the solvent load of≤20 liters of scopes.
3, in above-mentioned first and second schemes, the power of polarity can be referring to shown in Figure 1 for active ingredient (object).
The principle of the invention is (seeing shown in Figure 1):
1, select opposite with traditional solvent to the big solvent thinking of active ingredient solubility, the present invention selects a little less than the active ingredient dissolubility, and to respect to the strong impurity of active ingredient polarity or the impurity dissolubility a little less than the polarity strong solvent, by the diacolation effective component extracting.In this step, outside extract desolventizes, contain active ingredient and impurity, wherein, the polarity of impurity component depends on choice of Solvent, in other words, is strong polar impurity if select the impurity in the intensive polar solvent extract, and low pole impurity then is difficult for being extracted.On the contrary, if select weak polar solvent then impurity is low pole impurity, strong polar impurity then is difficult for being extracted.The purpose of doing like this is with the low-solubility of solvent to active ingredient, exchanges the selectivity to the strong and weak type of impurity polarity for, thereby simplifies further the technical difficulty of purifying, separating.Because when containing simultaneously with active ingredient in the extract when being the strong polar impurity at center and low pole impurity, it is the most difficult further purifying, separating, and only contain active ingredient in the extract and, can reduce difficulty with respect to strong impurity of active ingredient polarity or the impurity a little less than the polarity.
2,, select the mode of post absorption or liquid-liquid extraction to separate according to the contained active ingredient of extract and the characteristics of impurity component.Wherein, select when adopting extracting process to separate with to extract solvent polarity opposite, and immiscible solvent, by liquid-liquid extraction active ingredient is transferred in the extract from extract, and impurity still is retained in the extraction solvent, thereby can obtains crude extract.By way of example: choose the diacolation extraction at a lower temperature of the strong solvent of polarity at low pole active ingredient in the extraction, impurity component is strong polar impurity in the extract that obtain this moment, low pole impurity then is difficult for being extracted out, chooses very weak polar solvent continuous extraction again and shifts active ingredient.Just because of the low pole of the extractant of selecting, then strong polar impurity generally can or not transfer on a small quantity extractant mutually in, reach the purpose of purifying.Also can further handle extract, remove and carry impurity secretly, or absorption active ingredient is removed oil-soluble impurities by the continuous adsorption mode.Then just in time handle on the contrary for strong polarity active ingredient.In addition, extract also can separate by direct suction type.For the plant that is difficult to carry out Separation of Solid and Liquid, can be in the solvent of certain polarity with its powder suspension, another phase solvent directly extracts continuously, and the extract of outflow is constantly reached extraction separation purpose with the mode of the third solvent extraction transfer or absorption transfer and regenerated solvent cycling extraction.
3, because a little less than the dissolubility of solvent to active ingredient of using in the extraction process, active ingredient be extracted from plant fully needs quantity of solvent bigger.In order to overcome this defective, with extract with separates in reclaim or the solvent of regeneration drops into again and extracts and separating technology, thereby constitute the continuous circular flow pattern of extracting circulation and extraction cycle organic assembling, then can effectively address this problem.
In a word, the present invention is by force a core to select exchanging for the dopant type selectivity to the solvent a little less than the active ingredient dissolubility, and the means by successively separating strong polar impurity and low pole impurity improve effective component extracting technical merit and quality from natural plants.
Because the technique scheme utilization, the present invention compared with prior art has following advantage and effect:
1, the present invention selects low to active ingredient solubility in extraction and separation scheme, and the outstanding polarity type of impurity of selecting has substantive distinguishing features, doing the effect that is obtained like this is purification and the isolation technics difficulty that greatly reduces the road, back, make whole technology become simpler and fruitful, bigger but existing deficiency is the use amount of solvent.Yet, with extract with separates in reclaim or the solvent of regeneration drops into again and extracts and separating technology, overcome the big defective of solvent load thereby constitute the continuous circular flow of extracting circulation and separating cycle organic assembling, so had a practical value industrial.Consequent effect has significant technological progress with respect to conventional solution.
2, to extract the mode of separation continuously be to select the extraction separate mode of all kinds of solvents continuous flowing type for use in the present invention, organically combines, and reaches to extract to separate to finish synchronously.Obtain the solvent reclamation circulation with the transfer of the active ingredient in the continuous-flow, reduce the quantity of solvent that is used to have enough to meet the need greatly, reduce the solvent recovery regeneration of evaporation mode, cut down the consumption of energy and solvent consumption the raising security.In addition, recruitment is few, labour intensity is low, is control device with equipment (pump), reduces the control failure cost, and makes automation mechanized operation become possibility.
Description of drawings
Accompanying drawing 1 is for active ingredient of the present invention and impurity is strong, low pole distributes and selective extraction composition schematic diagram;
Accompanying drawing 2 is that tradition is extracted the technological process of production figure that separates plain sweet wormwood from artemisia leaf;
Accompanying drawing 3 extracts the technological process of production figure that separates plain sweet wormwood from artemisia leaf for the present invention;
Accompanying drawing 4 is that tradition is extracted the technological process of production figure that separates isoflavones from red clover;
Accompanying drawing 5 extracts the technological process of production figure that separates isoflavones from red clover for the present invention;
Accompanying drawing 6 extracts the another kind of technological process of production figure that separates isoflavones from red clover for the present invention.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: extract the method (qinghaosu production) of separating qinghaosu from artemisia leaf continuously
1, conventional production methods
Referring to Fig. 2, traditional approach selects for use No. 6 oil or benzinum to extract, and with silica gel absorption qinghaosu and strong polar impurity, removes oil-soluble impurities simultaneously, resolves again, and condensing crystallizing is recrystallized at last.The active ingredient average yield is 75%.The solvent use amount is big.
2, production method of the present invention
The present embodiment solvent selects thinking to guarantee in the leaching process that for using intensive polar solvent low pole impurity such as wax component are not suggested, the major impurity composition is strong polar component (for the object qinghaosu), during to the extract abstraction purification, select the very weak solvent of polarity again for use, guaranteeing that strong polar impurity is retained in the former extract, and qinghaosu is transferred in the weak polar solvent.Processing like this can be told artemislnin content continuously and be up to 95% crude product.Only need recrystallization once just can obtain qualified products, the condition selection rationally can obtain the rate of transform more than 90%.
Referring to Fig. 3, detailed process is for to place the diacolation jar with the artemisia leaf raw material, utilize measuring pump per hour being that (with methyl alcohol is example with the methyl alcohol of certain water content or ethanol continuously for the 1-4 flow velocity doubly of diacolation tank volume (liter), containing alcohol amount 30%-55%) heat exchanger of flowing through is heated to 20-35 ℃ of temperature, enter diacolation jar diacolation continuously extracts from the bottom, extract that flows out and benzinum are by continuous countercurrent extraction tower extraction exchange, with continuous the transferring in the benzinum of qinghaosu continuously.Sloughed the former extraction solution of qinghaosu, entered the diacolation jar through measuring pump again, constituted and extract circulation continuously.The benzinum that contains qinghaosu obtains coarse crystallization through concentrating to reclaim, and the benzinum that reclaims out is got back to extraction transfer qinghaosu in the tower again, constitutes the extraction transfer cycle.End until the recovery rate that reaches expection.Whole process is passed through the Frequency Converter Control flow rate of liquid, and all operation only needs can finish by startup, X button, and is simple and easy to control.General to extract that solvent selects with methyl alcohol be example, should not be higher than 50% the alcohol amount that contains, and descends along with containing the alcohol amount, and the coarse-grain quality improves, and the recrystallization loss descends, but be lower than 30% contain the alcohol amount time, extraction rate is slow excessively, does not have practical significance.
Embodiment two: extract the method (isoflavones production) of separating isoflavones from red clover continuously
1, conventional production methods
Referring to Fig. 4, processing procedures such as traditional approach is the height alcohol extract, concentrate, depositing in water, degreasing are obtained the product 20% or more, be again through the dissolution with solvents processing.
2, production method of the present invention
The present embodiment solvent selects thinking to guarantee in the leaching process that for using intensive polar solvent low pole impurity such as grease constituents are not suggested, the major impurity composition is strong polar component (for the object isoflavones), during to the extract abstraction purification, select the very weak solvent of polarity again for use, be retained in the former extract to guarantee strong polar impurity.Isoflavones components is transferred in the weak polar solvent.So processing can be told one step of isoflavones continuously and reaches the outlet content standard.
Referring to Fig. 5, detailed process is for to place the diacolation jar with the red clover raw material, utilize measuring pump per hour being that (methyl alcohol is example with the methyl alcohol of certain water content or ethanol continuously for the 1-4 flow velocity doubly of diacolation tank volume (liter), containing alcohol amount 30%-45%) heat exchanger of flowing through is heated to 20-35 ℃ of temperature, enter diacolation jar diacolation continuously extracts from the bottom, the mixed solvent of the continuous extract that flows out and benzinum and ethyl acetate (benzinum: ethyl acetate=1: 0.5～1: 2) by continuous countercurrent extraction tower extraction exchange, with continuous the transferring in the mixed solvent of isoflavones, sloughed the former extraction solution of isoflavones, enter the diacolation jar through measuring pump again, constitute and extract circulation continuously.The mixed solvent that contains isoflavones obtains coarse crystallization through concentrating to reclaim, and the mixed solvent that reclaims out is got back to extraction transfer isoflavones in the tower again, constitutes the extraction transfer cycle.End until the recovery rate that reaches expection.Whole process is passed through the Frequency Converter Control flow rate of liquid, and all operation only needs can finish by startup, X button, and is simple and easy to control.General to extract that solvent selects with methyl alcohol be example, should not be higher than 50% the alcohol amount that contains, and descends along with containing the alcohol amount, and the coarse-grain quality improves, and the recrystallization loss descends, but be lower than 20% contain the alcohol amount time, extraction rate is slow excessively, does not have practical significance.By adjusting the product that pure water content and extractant polarity can obtain 8%, 10%, 20%, 25%, 40% specification such as different content such as grade respectively, extract passes through the silica gel absorption regenerated solvent, cycling extraction, and silica gel is resolved can obtain more high-load product.
Embodiment three: extract the another kind of method (isoflavones production) of separating isoflavones from red clover continuously
Present embodiment selects weak polar solvent to extract, strong polar impurity is not extracted out as far as possible, the major impurity composition is low pole composition (for the object isoflavones), to extract silica gel continuous adsorption, impurity component is retained in the former extract, isoflavones components is adsorbed in the silica gel, and extraction is finished available ethanol and directly wash out product from silica gel, and processing like this can a step reach isoflavone content and meet export standard.
Referring to Fig. 6, detailed process is for to place the diacolation jar with the red clover raw material, utilize measuring pump per hour being that (benzinum: ethyl acetate=1: 0.5-1: 2) heat exchanger of flowing through is heated to 20-35 ℃ of temperature, enters diacolation jar diacolation continuously from the bottom and extracts with the mixed solvent of ethyl acetate and benzinum continuously for the 1-4 speed doubly of diacolation tank volume (liter).The extract Continuous Flow that flows out with continuous being adsorbed onto in the silica gel column chromatography of isoflavones, has been sloughed the former extraction solution of isoflavones through silica gel column chromatography, enters the diacolation jar through measuring pump again, is circulated to extract to finish.The silica gel that contains isoflavones obtains product through the ethanol elution processing.Whole process is passed through the Frequency Converter Control flow rate of liquid, and all operation only needs can finish by startup, X button, and is simple and easy to control.Adjust the product that the mixed solvent ratio can obtain 8%, 10%, 20%, 25%, 40% specification such as different content such as grade respectively.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1, the method for active ingredient in a kind of continuous extraction separating plant is characterized in that comprising following content:
(1), diacolation extracts
With the plant that contains active ingredient is raw material, selection to the active ingredient dissolubility a little less than, and to respect to the strong solvent of the strong impurity of active ingredient polarity or the impurity dissolubility a little less than the polarity for extracting solvent, extract continuously in the mode of solvent continuous-flow by continuous diacolation method and to contain active ingredient and with respect to the strong impurity of active ingredient polarity or the extract of the impurity a little less than the polarity; Described extraction solvent to the complete dissolubility of effective components in plants in following scope: dissolve active ingredient needs 〉=10 liter in the per kilogram plant fully, the solvent load of＜35 liters of scopes;
(2), extraction is shifted
With the extract is object, select on the contrary with the extraction solvent polarity, and immiscible solvent is extractant, by the mode of continuous extration method with solvent continuous-flow, active ingredient in the extract transferred to obtain extract in the extractant, and impurity is retained in and extracts in the solvent;
(3), circulation combination continuously
The extraction solvent that reclaims from extraction or regenerate drops into diacolation again and extracts, and constitutes continuous extraction circulation with this; Purified or/and concentrated coarse crystallization or the product of obtaining of extract or/and reclaim concentrating or the extractant of regeneration drops into the extraction transfer again, constitutes continuous extraction cycle with this from purifying.
2, method according to claim 1, it is characterized in that: described purifying is to be object with the extract, selected adsorbent, adopt column chromatography method with extract continuous-flow mode selective absorption active ingredient, the desorbed solution that the parsing adsorbent obtains is directly as product or again through concentrated object coarse crystallization or the product of obtaining; Impurity is retained in the extractant in the adsorption process, and the regeneration extractant is used for cycling extraction.
3, the method for active ingredient in a kind of continuous extraction separating plant is characterized in that comprising following content:
(1), diacolation extracts
With the plant that contains active ingredient is raw material, selection to the active ingredient dissolubility a little less than, and to respect to the strong solvent of the strong impurity of active ingredient polarity or the impurity dissolubility a little less than the polarity for extracting solvent, extract continuously in the mode of solvent continuous-flow by continuous diacolation method and to contain active ingredient and with respect to the strong impurity of active ingredient polarity or the extract of the impurity a little less than the polarity; Described extraction solvent to the complete dissolubility of effective components in plants in following scope: dissolve active ingredient needs 〉=10 liter in the per kilogram plant fully, the solvent load of＜35 liters of scopes;
(2), absorption is shifted
With the extract is object, and selected adsorbent adopts column chromatography method with extract continuous-flow mode selective absorption active ingredient, and the desorbed solution that the parsing adsorbent obtains is directly as product or again through the concentrated object coarse crystallization that obtains; Impurity is retained in and extracts in the solvent in the adsorption process, and the extraction solvent of recovery or regeneration drops into diacolation again and extracts, and constitutes continuous extraction circulation with this.
4, according to claim 1 or 3 described methods, it is characterized in that: described extraction solvent to the complete dissolubility of effective components in plants in following scope: dissolve active ingredient needs 〉=12 liter in the per kilogram plant fully, the solvent load of≤25 liters of scopes.
5, method according to claim 4 is characterized in that: described extraction solvent to the complete dissolubility of effective components in plants in following scope: dissolve active ingredient needs 〉=15 liter in the per kilogram plant fully, the solvent load of≤20 liters of scopes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102697820A (en) * | 2012-05-28 | 2012-10-03 | 西北大学 | Poria peel extract and application of poria peel extract in preparation of diuretic medicines |
| CN112915583A (en) * | 2021-02-01 | 2021-06-08 | 金华寿仙谷药业有限公司 | Purification system and purification process of lotus leaf alkaloid monomer |
| CN113634011A (en) * | 2021-08-24 | 2021-11-12 | 伽能生物科技(上海)有限公司 | Production integrated system of red pruned pine and red pruned refined extract composition, red pruned pine and red pruned refined extract composition and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083729A (en) * | 1995-10-26 | 2000-07-04 | Metabolix, Inc. | Methods for isolating polyhydroxyalkanoates from plants |
| CN2782184Y (en) * | 2005-04-30 | 2006-05-24 | 苏州市兴科现代中药工艺装备开发有限公司 | Extraction and purification appts. for effective component of plants |
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2006
- 2006-11-07 CN CNB2006100975717A patent/CN100434134C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102697820A (en) * | 2012-05-28 | 2012-10-03 | 西北大学 | Poria peel extract and application of poria peel extract in preparation of diuretic medicines |
| CN102697820B (en) * | 2012-05-28 | 2014-07-09 | 西北大学 | Poria peel extract and application of poria peel extract in preparation of diuretic medicines |
| CN112915583A (en) * | 2021-02-01 | 2021-06-08 | 金华寿仙谷药业有限公司 | Purification system and purification process of lotus leaf alkaloid monomer |
| CN113634011A (en) * | 2021-08-24 | 2021-11-12 | 伽能生物科技(上海)有限公司 | Production integrated system of red pruned pine and red pruned refined extract composition, red pruned pine and red pruned refined extract composition and preparation method thereof |
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Assignee: Huayuan Hengyuan Plant Biochemistry Co., Ltd. Assignor: Xingke Chinese Medicine Technology & Equipment Inc. Contract fulfillment period: 2009.8.15 to 2014.8.15 contract change Contract record no.: 2009430000067 Denomination of invention: Process of extracting and separating effective components from plant continuously Granted publication date: 20081119 License type: Exclusive license Record date: 2009.9.18 |
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