CN105037153A - Method for preparing DBP through waste liquid generated by antarctic krill alkaloid extraction - Google Patents
Method for preparing DBP through waste liquid generated by antarctic krill alkaloid extraction Download PDFInfo
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- CN105037153A CN105037153A CN201510439770.0A CN201510439770A CN105037153A CN 105037153 A CN105037153 A CN 105037153A CN 201510439770 A CN201510439770 A CN 201510439770A CN 105037153 A CN105037153 A CN 105037153A
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- C07—ORGANIC CHEMISTRY
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Abstract
The invention discloses a method for preparing DBP through waste liquid generated by antarctic krill alkaloid extraction. The method mainly includes the steps that alkaloid is extracted from antarctic krill through hydrochloric acid alcohol, petroleum ether is used for removing ester, aqueous ammonia is used for adjusting pH and then chloroforming is conducted for extracting the alkaloid. Impurities of the obtained waste liquid are removed through ethyl acetate, the ratio of petroleum ether to ethyl acetate obtained through n-butanol extraction and column chromatography separation is 1:3, elution, collection and spin drying are conducted, and dibutyl phthalate with the purity larger than or equal to 97% is obtained through HPLC preparation and ablution. According to the method, the dibutyl phthalate is prepared by means of the waste liquid of antarctic krill alkaloid extraction, the waste liquid of antarctic krill alkaloid extraction is fully used, and use is environmentally friendly. Besides, the prepared dibutyl phthalate has good application value, the product chain of an antarctic krill product is prolonged, additional value of the product is increased, and the purity of the extracted dibutyl phthalate is over 97%.
Description
Technical field
The present invention relates to a kind of method utilizing krill to extract alkaloidal waste liquid to prepare DBP, belong to chemistry, medicine and field of food.
Technical background
Dibutyl phthalate (DibutylPhthalate, DBP) is the one in phthalate, is mainly used as the softening agent of nitrocotton, cellulose acetate, fluorinated ethylene propylene, polystyrene etc.Polyvinyl chloride, flexibility that modified styrene polymer is good can be given.Due to its cheaper and processing characteristics is good, use at home widely.These product are fine plasticizer of nitrocellulose, and gelling ability is strong.For cellulose nitrate coating, there is good ramollescence.Stability, resistance to deflection, tackiness and water-repellancy are all excellent.In addition, these product also can be used as poly-ethyl acetate, Synolac, ethyl cellulose and chloroprene rubber, natural rubber softening agent, also can be used for manufacturing paint, caking agent, leatheroid, printing-ink, shatter proof glass, fuel, sterilant, perfume solvent, plant lubricant etc.
In plasthetics packaging, people often can touch dibutyl phthalate, have a lot of food may cause the stripping of dibutyl phthalate and infiltrate in food in the process of processing, heating, packaging, splendid attire in life.
The plastic bottle of plastic toy, the preservative film covering food microwave heating, splendid attire food, to eat food or therapeutic medical plastic gloves or transfusion bags etc., all contain dibutyl phthalate.
Soft plastics toy containing dibutyl phthalate and articles for children and children have Long contact time that the stripping quantity of dibutyl phthalate will be caused to exceed security level, can endanger liver and the kidney of children, also can cause children's sexual precocity.
Dibutyl phthalate plays the effect of similar female hormone in human body and animal body, can disturbance endocrine, man semen amount and sperm quantity are reduced, Sperm Motility is low, sperm morphology is abnormal, serious meeting causes carcinoma of testis, is to cause man's reproductive problems " arch-criminal ".
In makeup, the dibutyl phthalate content of nail varnish is the highest, and the fragrance ingredient of a lot of makeup is also containing this material.This material in makeup can be entered in body by the respiratory system of women and skin, if excessive use, can increase the probability that women suffers from breast cancer, and also can jeopardize the reproductive system of the boy baby of their following fertility.
Krill is the crustacean of one way of life in waters, the Antarctica, lives in the mode of trooping, and density is up to 10,000 ~ 30,000/M sometimes
3, they may be the most successful animal species on the earth, according to statistics nearly 5 ~ 5,000,000,000 tons (having larger difference because statistical method is different).
Annual about 100,000 tons of current krill fishery, wherein 80% is caught by Japan, is also destroyed catch totally due to the Southern Oceans baleen whale that take krill as main fresh food.Relevant scientific man once approximately has 1.5 hundred million tons every year according to the food ration estimation of vigorous cetacean in period to krill class, and due to the decline of cetacean resource, remaining krill can for catching.Fishery productions whole every year is in the world 0.99 hundred million ton, and this indicates that krill has larger utilized space.China is souning out catches krill to improve fishing for and relevant marine technical of krill.Krill fish for the beginning indicating deep process technology in a large number.At Japanese krill mostly as cooking, in other countries then mainly as the feed of fishery and the erbium material of fish.The research of krill high added value is the research core of its deep processing.
Krill is containing inorganic fluorine, and fluorine is poisonous, can not directly eat.Therefore, the krill after fishing for is processed into grease (as euphausia superba sauce) or is extracted by activeconstituents useful to the mankind in its body by people, carries out precision work utilization.The extraction of applicant's long campaigns krill active substance of the present invention, finds in research process, and the remaining waste liquid after krill alkaloid extracts also has plurality of active ingredients.If can make full use of these compositions, be not only conducive to environmental protection, but also can product chain be extended, improve value-added content of product.
Summary of the invention
Object of the present invention is exactly to provide a kind of method utilizing krill to extract alkaloidal waste liquid to prepare DBP.
To achieve these goals, the present invention adopts following technical scheme:
The method utilizing krill to extract alkaloidal waste liquid to prepare DBP, step is as follows:
(1) extract in alkaloidal waste liquid to krill and add ethyl acetate, mixing, stratification, obtains upper strata ethyl acetate layer and lower aqueous solution, and the volume ratio of the add-on that ethyl acetate is each and waste liquid is (1-1.5): 4;
(2) in lower aqueous solution, add n-butanol extraction, mixing, stratification, isolates n-butanol layer, and concentrated, obtain paste, the volume ratio of the add-on that propyl carbinol is each and lower aqueous solution is (1-2): 4;
(3) in the silica gel after activation, petroleum ether-ethyl acetate mixed solution is added, mix thoroughly, dress post, using the paste of step (2) as sample loading, silica gel consumption is 30-35 times of the sample quality of loading, carries out wash-out, flow velocity 1-2ml/min respectively with the petroleum ether-ethyl acetate mixed solution that volume ratio is 3:1-1:3 as elutriant, the elutriant collecting petroleum ether-ethyl acetate=1:3 revolves steaming, must containing the paste of dibutyl phthalate;
Concrete, in step (1), described krill extracts alkaloidal waste liquid, refers to that krill is extracted by the ethanolic soln containing 5% (volume fraction) acetic acid, obtains medicinal extract, add H in medicinal extract after extracting solution is concentrated
2sO
4the aqueous solution, then add sherwood oil and extract, the lower aqueous solution after stratification is the waste liquid after extracting alkaloid through adding ammoniacal liquor and the chloroform upper water solution again after layering.
Preferably, in step (1), the number of times adding ethyl acetate extraction is 2-4 time, and the volume ratio of the add-on that ethyl acetate is each and waste liquid is 1:4.The extraction time of ethyl acetate is elected as 2-4 time, not only effectively isolates krill and extracts dibutyl phthalate in alkaloidal waste liquid, the energy dissipation that the increase that can also as far as possible reduce extraction time brings.
Preferably, in step (2), the number of times adding n-butanol extraction is 4-6 time, and the volume ratio of the add-on that propyl carbinol is each and lower aqueous solution is 1:4.
Preferably, in step (3), the method that the activation of silica gel adopts is that silica gel is activated 12h under 110 DEG C of conditions.
Preferably, in step (3), the order number of described silica gel is 200-300 order.The silica gel order number that the present invention selects is 200-300 order, and separating effect is better, and elution speed is moderate, and the two reaches effective balance.
Preferably, in step (3), in described petroleum ether-ethyl acetate mixed solution, the volume ratio of sherwood oil and ethyl acetate is 3:1.
Preferably, in step (3), the ratio of silica gel add-on after described petroleum ether-ethyl acetate mixed solution and activation is 1g:(1-2) ml.The present invention adopts wet method to fill post, after first being mixed thoroughly by the silica gel appropriate solvent (petroleum ether-ethyl acetate mixing solutions) after activation, then inserts pillar; The add-on of silica gel and solvent directly affects the effect that wet method fills post, the present invention is after condition optimizing, the ratio of silica gel add-on after petroleum ether-ethyl acetate mixed solution and activation is 1g:(1-2) ml, the pillar of filling under this condition is durable, and does not have bubble.
Preferably, in step (3), the elutriant that wash-out adopts is respectively:
Volume ratio is the petroleum ether-ethyl acetate mixing solutions of 3:1, and the consumption of elutriant is 0.5L:2g with the ratio of the sample quality of loading;
Volume ratio is the petroleum ether-ethyl acetate mixing solutions of 1:1, and the consumption of elutriant is 0.5L:2g with the ratio of the sample quality of loading;
Volume ratio is the petroleum ether-ethyl acetate mixing solutions of 1:3, and the consumption of elutriant is 1.0L:2g with the ratio of the sample quality of loading.
It is very crucial that elutriant and elution requirement are selected the separating effect for column chromatography, and the present invention adopts petroleum ether-ethyl acetate as elutriant, can effectively be separated by dibutyl phthalate.
(7) paste that step (6) obtains is dissolved in acetonitrile, solution 0.45 μm of filtering with microporous membrane, C on preparation HPLC
18reverse semipreparative column (YMC-packODS-A, 10 μm, 10mm × 250mm) upper separation, moving phase is 80% acetonitrile-water system wash-out, flow velocity is 3.0ml/min, and sample size is 2ml/ time, determined wavelength 210nm, collect to being 4.145mm peak when retaining, this peak is dibutyl phthalate (DBP).Collect liquid N
2dry up.Type HPLC detects by analysis, and DBP purity is more than 97%.Through above process, 200g does the South Pole separable DBP of squama shrimp and is about 5mg.
Accompanying drawing explanation
Fig. 1 be embodiment 1 product after purification high-efficient liquid phase chromatogram.
Beneficial effect of the present invention:
1. the waste liquid that the present invention utilizes krill alkaloid to extract first has prepared dibutyl phthalate, achieve and making full use of of waste liquid is extracted to krill alkaloid, not only be beneficial to environmental protection, and the dibutyl phthalate of preparation has good using value, extend the product chain of krill product, add value-added content of product, the dibutyl phthalate purity extracted reaches more than 97%.
2. the krill after extracting can be used further to produce other products, and eliminates the harm of DBP, and the DBP of extraction may be used for industrial production.
3. South Pole squama shrimp DBP be extracted in the existence of eliminating DBP in the preparation of the South Pole other active substances of squama shrimp and harm has important value.In research Members In Antarctic Environment and South Pole squama shrimp growth, reproduction, having important value in physiology, is also the important references of South Pole squama shrimp as food consumption amount.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1.
Claim 200g dry shrimp, add 1400ml95% ethanol (wherein containing 7ml acetic acid) 4-10 DEG C cold soaking 4 days, coarse filtration.Filter residue repeats above process cold soaking once again.After twice filtrate merges, essence filters to obtain filtrate, steams to obtain paste 58g (50 DEG C of relative densities surveying paste are 1.3) through revolving.
300mlpH=3.5H is added in paste
2sO
4the aqueous solution, mixing, enters separating funnel, then adds 100ml sherwood oil, mix static, separate upper strata petroleum ether solution, lower aqueous solution, then repeats above procedure extraction once with amount (V) sherwood oil, about obtains 300ml lower aqueous solution.
Lower aqueous solution enters separating funnel, adds the mixing of 100ml ammoniacal liquor wherein, then adds 100ml chloroform, mixing, static layering (upper strata is yellow, and lower floor is faint yellow).2 these separatory processes are repeated again with chloroform.Obtain the chloroform solution of lower floor for extracting alkaloid, and obtain upper water solution (yellow thick) about 400ml, be krill and extract alkaloidal waste liquid.
To upper strata 400ml krill extract in alkaloidal waste liquid add ethyl acetate be about 100ml mixing, static layering obtains upper strata ethyl acetate layer and lower aqueous solution, then with amount ethyl acetate repetition separatory extract 2 times, totally 3 times, obtain lower aqueous solution.
In lower aqueous solution, add propyl carbinol 100ml, mixing, static layering, obtain upper n-butanol layer and lower aqueous solution respectively.Repeat above leaching process 4 times, totally 5 times with amount propyl carbinol, n-butanol layer is merged about 600ml and revolve steaming, obtain paste 25g.
Get 66g200 ~ 300 object silica gel, add appropriate petroleum ether-ethyl acetate (3:1) mixed solution after 110 DEG C of activation 12h and mix thoroughly.Joined in the silicagel column of 3cm × 30cm, application of sample 2g after wet method dress post completes, with sherwood oil: ethyl acetate=3:1 (0.5L), 1:1 (0.5L), 1:3 (1.0L) wash-out, flow velocity 1-2ml/min.Every 200ml collects an elutriant.The elutriant of petroleum ether-ethyl acetate=1:3 is collected and revolves steaming, must containing the paste 0.4mg of dibutyl phthalate 46.5%.
Paste is dissolved in acetonitrile, solution 0.45 μm of filtering with microporous membrane.C on preparation HPLC
18reverse semipreparative column (YMC-packODS-A, 10 μm, 10mm × 250mm) is upper to be separated, and moving phase is 80% acetonitrile-water system wash-out.Flow velocity is 3.0ml/min, and sample size is 2ml/ time, determined wavelength 210nm, and collecting retention time is 4.145mm peak.This peak is dibutyl phthalate (DBP).Collect liquid N
2dry up.Type HPLC detects by analysis, and as shown in Figure 1, DBP purity is more than 97%.Through above process, 200g does the South Pole separable DBP of squama shrimp and is about 5mg.
In DBP preparation process, all avoid contact plasthetics, adopt glassware without exception,
Whole organic solvent is used to carry out rotary evaporation by usage quantity, to residue N to the preparation process such as sherwood oil, normal hexane, ammoniacal liquor, acetic acid, chloroform, propyl carbinol, ethyl acetate used
2dry up detection, use the existence not finding DBP in solvent.
Experiment is determined, the DBP that preparation is extracted in experiment confirms from South Pole squama shrimp.
Embodiment 2
All steps with example 1, difference be propyl carbinol prepare paste column chromatography time be applied sample amount be 3g, the dibutyl phthalate of preparation is that the result that detects of 0.6mg, HPLC is as embodiment 1.
The specific embodiment of the present invention is described although above-mentioned in conjunction with the embodiments; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. the method utilizing krill to extract alkaloidal waste liquid to prepare DBP, it is characterized in that, step is as follows:
(1) extract in alkaloidal waste liquid to krill and add ethyl acetate, mixing, stratification;
(2) in lower aqueous solution, add n-butanol extraction, mixing, stratification, isolates n-butanol layer, concentrated, obtains paste;
(3) in the silica gel after activation, petroleum ether-ethyl acetate mixed solution is added, dress post, using the paste of step (2) as sample loading, carries out wash-out with petroleum ether-ethyl acetate mixed solution, collect elutriant and revolve steaming, must containing the paste of dibutyl phthalate.
2. the method for claim 1, is characterized in that, in described step (1), krill extracts alkaloidal waste liquid, refers to that krill is extracted by the ethanolic soln containing volume fraction 5% acetic acid, obtains medicinal extract, add H in medicinal extract after extracting solution is concentrated
2sO
4the aqueous solution, then add sherwood oil and extract, the lower aqueous solution after stratification is the waste liquid after extracting alkaloid through adding ammoniacal liquor and the chloroform upper water solution again after layering.
3. the method for claim 1, is characterized in that, in described step (1), the number of times adding ethyl acetate extraction is 2-4 time, and the volume ratio of the add-on that ethyl acetate is each and waste liquid is (1-1.5): 4.
4. the method for claim 1, is characterized in that, in described step (2), the number of times adding n-butanol extraction is 4-6 time, and the volume ratio of the add-on that propyl carbinol is each and lower aqueous solution is (1-2): 4.
5. the method for claim 1, is characterized in that, in described step (3), the method that the activation of silica gel adopts is that silica gel is activated 12h under 110 DEG C of conditions.
6. the method for claim 1, is characterized in that, in described step (3), the order number of silica gel is 200-300.
7. the method for claim 1, is characterized in that, in described step (3), in petroleum ether-ethyl acetate mixed solution, the volume ratio of sherwood oil and ethyl acetate is 3:1.
8. the method for claim 1, is characterized in that, in described step (3), the ratio of silica gel add-on after petroleum ether-ethyl acetate mixed solution and activation is 1g:(1-2) ml.
9. the method for claim 1, is characterized in that, in described step (3), the elutriant that wash-out adopts is respectively:
Volume ratio is the petroleum ether-ethyl acetate mixing solutions of 3:1, and the consumption of elutriant is 0.5L:2g with the ratio of the sample quality of loading;
Volume ratio is the petroleum ether-ethyl acetate mixing solutions of 1:1, and the consumption of elutriant is 0.5L:2g with the ratio of the sample quality of loading;
Volume ratio is the petroleum ether-ethyl acetate mixing solutions of 1:3, and the consumption of elutriant is 1.0L:2g with the ratio of the sample quality of loading.
10. the method for claim 1, is characterized in that, in described step (3), described silica gel consumption is 30-35 times of the sample quality of loading, elution flow rate 1-2ml/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188066A (en) * | 2016-07-19 | 2016-12-07 | 山东师范大学 | The extraction of a kind of Antarctic krill non-phenol alkalescence alkaloid and detection method |
| CN106279179A (en) * | 2016-07-19 | 2017-01-04 | 山东师范大学 | The extraction purification of a kind of Antarctic krill DTDP and detection method |
| CN106279180A (en) * | 2016-07-19 | 2017-01-04 | 山东师范大学 | Pyrrolo-[1,2 a] pyrazine 1,4 diketone in a kind of Antarctic krill, the extraction purification of hexahydro 3 (2 methyl-propyl) and detection method |
| CN106279181A (en) * | 2016-07-19 | 2017-01-04 | 山东师范大学 | The extraction purification of a kind of Antarctic krill non-phenol alkalescence alkaloid and detection method |
| CN108450648A (en) * | 2018-03-08 | 2018-08-28 | 佛山汇沐化学科技有限公司 | A kind of extracting method of grub biological alkali and its application |
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| CN102041166A (en) * | 2011-01-20 | 2011-05-04 | 山东师范大学 | Method for extracting krill oil with high phosphatide content from Antarctic krills |
| CN102559366A (en) * | 2012-02-21 | 2012-07-11 | 山东师范大学 | Method for preparing phosphatidyl ethanolamine-enriched Neptune krill oil |
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- 2015-07-23 CN CN201510439770.0A patent/CN105037153B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102041166A (en) * | 2011-01-20 | 2011-05-04 | 山东师范大学 | Method for extracting krill oil with high phosphatide content from Antarctic krills |
| CN102559366A (en) * | 2012-02-21 | 2012-07-11 | 山东师范大学 | Method for preparing phosphatidyl ethanolamine-enriched Neptune krill oil |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188066A (en) * | 2016-07-19 | 2016-12-07 | 山东师范大学 | The extraction of a kind of Antarctic krill non-phenol alkalescence alkaloid and detection method |
| CN106279179A (en) * | 2016-07-19 | 2017-01-04 | 山东师范大学 | The extraction purification of a kind of Antarctic krill DTDP and detection method |
| CN106279180A (en) * | 2016-07-19 | 2017-01-04 | 山东师范大学 | Pyrrolo-[1,2 a] pyrazine 1,4 diketone in a kind of Antarctic krill, the extraction purification of hexahydro 3 (2 methyl-propyl) and detection method |
| CN106279181A (en) * | 2016-07-19 | 2017-01-04 | 山东师范大学 | The extraction purification of a kind of Antarctic krill non-phenol alkalescence alkaloid and detection method |
| CN106279180B (en) * | 2016-07-19 | 2018-03-23 | 山东师范大学 | The diketone of pyrrolo- [1,2 a] pyrazine 1,4, the extraction purification and detection method of hexahydro 3 (2 methyl-propyl) in a kind of krill |
| CN108450648A (en) * | 2018-03-08 | 2018-08-28 | 佛山汇沐化学科技有限公司 | A kind of extracting method of grub biological alkali and its application |
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