CN101284857A - Process for abstracting biological pesticide avermectin from biochemical wastes - Google Patents
Process for abstracting biological pesticide avermectin from biochemical wastes Download PDFInfo
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- CN101284857A CN101284857A CNA2008100164006A CN200810016400A CN101284857A CN 101284857 A CN101284857 A CN 101284857A CN A2008100164006 A CNA2008100164006 A CN A2008100164006A CN 200810016400 A CN200810016400 A CN 200810016400A CN 101284857 A CN101284857 A CN 101284857A
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- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
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Abstract
The invention relates to a method for extracting and making avermectin by biochemical waste. The method comprises the following steps that: methanol is added in biochemical waste to carry out alcohol extraction, filtration and dichloroethene extraction; and dichloroethene extract is dried by waterless Na2SO4 and then is concentrated at the temperature of between 38 and 45 DEG C after filtration to obtain avermectin product. The invention, adopting biochemical waste water as a raw material to make biochemical pesticide, not only opens up the source of novel cheap raw material to control environmental pollution, but also substantially reduces production cost.
Description
Technical field
The present invention relates to a kind of method of utilizing biochemical wastes to extract the biochemical pesticide Avrmectin.
Background technology
Biological pesticide is the goods that directly utilize living organisms composition or biogenic natural active matter to process, and is raw material based on natural agricultural byproducts (plant, animal proteinum) mainly usually, makes by microbial fermentation.Characteristics such as it is strong that biological pesticide has specificity, active high, environmentally safe, comparatively safe to non-target biology, and development and utilization measure is many, and the choice of exploitation is big are described as public nuisance-free agricultural chemicals.Therefore biological pesticide is more suitable for enlarging production application in modern agriculture integrated pest management strategy than chemical synthetic pesticide.
Avrmectin (Avermectin) is the dual-purpose microbiotic of a kind of novel farming animals, belongs to macrolide antibiotic class insecticidal/acaricidal agent, is the fermentating metabolism product of soil microorganisms grey Streptomycin sulphate (St rentomyces avermitilis), possesses nuisanceless characteristic.The Avrmectin chemical structure is the macrolide of band disaccharide side chain, is made up of 8 components such as A1a, A1b, A2a, A2b, B1a, B1b, B2a and B2b, and the biological activity of B component is better than the A component in 8 components, and is wherein the strongest with the B1a composition activity.1976, Merck company exploitation Avrmectin (AVM), ivermectin (IVM) and series product thereof.AVM puts goods on the market in 1985 as agricultural chemicals, IVM puts goods on the market in 1981 as veterinary drug, since AVM and series product listing thereof, countries in the world scientist and researchist think that its discovery and application are to have continued since the penicillin microbiotic science to the mankind's another huge contribution, simultaneously, to the development and the exploitation of Avrmectin agricultural chemicals, also become the focus of human development biological pesticide.
China introduces the separation Avrmectin the end of the eighties and produces plain bacterial classification Streptomycin sulphate (St rentomyces avermitilis), 1994, China first AVM product agricultural Avermectin in north (Biocidal miticide) agricultural company in Beijing is born, and this is AVM first high-tech product from former medicine to preparation that Chinese finish; Nineteen ninety-five, " A Fuding " agricultural company in Beijing succeeds in developing, and this is that China develops the AVM product for animals that comes out at first voluntarily.
Avrmectin has very high biological activity to the harmful mite and the insect of multiple kinds of crops, it is a kind of good microbiotic Insecticidal and acaricidal agent, controlling object mainly is cabbage caterpillar, small cabbage moth, prodenia litura, bollworm, oriental tobacco budworm, aphid, wood louse, small heart-eating peach worm, liriomyza bryoniae, leaf dive fly, gallfly, mite class etc., has wide spectrum, efficient, low residue and to characteristics such as people and animals and environmental safeties.Because its mechanism of action uniqueness can effectively be prevented and treated the insect and the evil mite that Insecticidal and acaricidal agent commonly used are produced resistance, is one of comparatively ideal pesticide species in the current Agricultural pests integrated control.
Avrmectin is a kind of nerve poison, and mite class and insect are had stomach toxicity and action of contace poison, can not kill ovum.Its mechanism of action is by disturbing the activity of insect nervous physiology, stimulate polypide to produce γ 2 aminobutyric acids, thereby the transmittance process of blocking-up motorius information, the signal of insect central nervous system can not be accepted by the passive movement neurone, thereby cut off the contact of motorius and muscle, make insect paralysis, food refusal, slow-action or motionless rapidly in several hours, promptly dead after 24 days.Because of not causing that insect dewaters rapidly, so the Avrmectin lethal effect is slower.Though Avrmectin is so fast not as some nerve poison to the drug effect of worm, mite, it benumbs insect, makes it seldom to get food, reaches the purpose that makes crop exempt from insect pest.Though Avrmectin has direct action of contace poison to predatory insect and insect parasite, but because of the Avrmectin that sprays leaf surface can decompose dissipation rapidly, and but the activeconstituents long period in the infiltration plant parenchyma is present in the plant tissue and conduction is arranged, so the insect tool to the evil mite and the food harm of diving is long-lasting, and to predatory insect and insect parasite safety.
Avermitilis strain have contact toxicity, but stomach poison activity is better, and 2～3 days insecticidal effects reach the climax after the dispenser, about 7～15 days of lasting period.Wherein the mite class reaches 30～45 days, and resistance of rainwater washing against.Avrmectin does not have ovicidal action, but it can infiltrate in the plant leaf tissue, forms the anther sac standing storage, and " the active transfer ", kills the leaf mining larva of ensconcing in the leaf, and suppresses newborn larva and slip in the leaf.It can make the appetite of the female insect of soup on the contact blade and egg laying amount descend.
Chinese patent file CN1294197 (00130233.7) discloses a kind of novel process of fermentative Production Avrmectin, it is characterized in that using during the fermentation can producing Avrmectin and Avrmectin being secreted into the outer microorganism A Fumai Streptomycin sulphate CCTCC NO:M200028 of mycetocyte.Can reduce production costs, realize the semicontinuous of Avrmectin or continuously ferment.
Chinese patent file CN1923840 (200610048349.8) discloses a kind of avermectin extraction technology, it be with the dried mycelium of Avrmectin and methyl alcohol or ethanol with 1: 5～1: 10 weight ratio in the lixiviate in-tank mixing, after continuing to stir 3～6 hours under 20～25 ℃ of temperature, make vat liquor; Under 0.1～0.6Mpa pressure, be that the filter membrane system of 10 μ m～2nm filters with vat liquor again by the aperture; Send into the work in-process system of processing by the filtrate of filter membrane system, a raffinate part is returned the lixiviate jar, and another part by the filter membrane system circulating filtration, filters when finishing residue in the emptying lixiviate jar behind recycle pump.Owing to adopt technology of the present invention and adopt closed membrane filtration system filtration, can separate, clarify the Avrmectin vat liquor effectively, filtration velocity is fast, filtering accuracy height, technological process can shorten 6～12 hours every day, and yield can improve 5～7%, energy consumption is low, reduce production cost, greatly improved Working environment simultaneously, had the significant social economic benefit.
Up to now, Shang Weiyou utilizes biochemical wastes to extract the report of preparation Avrmectin.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of biochemical wastes that utilizes to extract the method for preparing Avrmectin.
Summary of the invention
At present the numerous L-glutamic acid producer of China is many is that carbon source, liquefied ammonia are that nitrogenous source ferments with rough glucose; Extract and purifying L-glutamic acid by the isoelectric point crystallizing technology then; Remaining liquefied ammonia then obtains recycling by forming sulfate of ammoniac in the fermented liquid.To extract the later residue of ammonium sulfate promptly as liquid waste disposal, this class waste liquid is biochemical wastes of the present invention.
In order to make full use of biochemical wastes, turn waste into wealth, the present inventor detects by the content to Avrmectin in the above-mentioned biochemical wastes, but be surprised to find that the Avrmectin that contains extracted amount in this waste, prepare the method for Avrmectin through testing the extraction that proposes a kind of processing ease, ideal yield coefficient repeatedly.Because the output of these waste liquids is very big, price very low (about 200 yuan/ton).And the market value of Avrmectin is 1,000,000 yuan/ton at present, extracts the production prices that can reduce Avrmectin greatly with this raw material.
Detailed Description Of The Invention
Biochemical wastes of the present invention is to be that carbon source, liquefied ammonia are that nitrogenous source ferments with rough glucose, extracts in the fermented liquid behind the L-glutamic acid remaining liquefied ammonia and reclaims and form the later waste liquid of ammonium sulfate.
A kind of biochemical wastes that utilizes extracts the method for preparing Avrmectin, comprises ethanol-extracted, filtration, extraction, and concrete steps are as follows:
(1) add methyl alcohol in biochemical wastes, fully mixed the extraction separated and kept the upper strata extracting solution, adds methyl alcohol again in lower floor's thing, and same repeatedly operation is extracted 2-3 time, merges alcohol extract; Wherein, biochemical wastes with the ratio of methyl alcohol is: (20-40) g: (50-100) ml.
(2) alcohol extract with step (1) gained filters,
(3) the 10%NaCl solution of adding 100-150ml in the filtrate of step (2) is used dichloromethane extraction 2-3 time, combining extraction liquid, and waste liquid is recycling,
(4) with dichloromethane extraction liquid through anhydrous Na
2SO
4Drying is filtered, and 38-45 ℃ concentrates, and gets the Avrmectin product.
Preferably, fully mixed extraction of above-mentioned steps (1) is to adopt ultrasonic oscillation extraction 30-40min, also can stir and extract 30-60min.
The filtration of above-mentioned steps (2) selects for use the plate and frame filter to filter or the B suction filtration.
Extracting the Avrmectin product that obtains for step (4) measures by high performance liquid chromatography: measurement result (as shown in Figure 2).
Waste liquid after above-mentioned steps (3) dichloromethane extraction also can be in order to produce 10% amino acid foliage fertilizer through further processing.
The inventive method is extracted the Avrmectin purity 2～4% of preparation, approaches the content of the Avrmectin that present biological process produces.
The inventive method is extracted the Avrmectin of preparation, adds certain solvent and emulsifying agent and makes 0.5% abamectin emulsifiable concentrate, use as antibiotic insecticide, and be one of comparatively ideal pesticide species in the current Agricultural pests integrated control.
Extract waste water behind the Avrmectin by the inventive method, can be all in order to produce 10% amino acid foliage fertilizer, avoid producing secondary pollution.
Excellent results compared with prior art of the present invention is as follows:
1, Avrmectin is to utilize biochemical residue, by extracting the biological pesticide that bacterial strain regeneration metallization processes is produced, raw material is pure biogenic, product has broad-spectrum high efficacy, resists resistance, lasting period length, low residue, easily degraded, to the characteristic of people and animals and ecotope high safety, be one of comparatively ideal biological pesticide kind in the current Agricultural pests integrated control.
2, with the biochemical waste water be raw material,, curb environmental pollution that built environment friendly society is significant for the development and use waste resource.
3, utilize biochemical waste water to make biochemical pesticide, not only opened up novel cheap raw material source, and reduced production costs significantly for raw material.
4, biochemical residue utilization is abundant.Extract the waste water behind the Avrmectin, all, do not produce secondary pollution in order to produce 10% amino acid foliage fertilizer.
Description of drawings
Fig. 1 Avrmectin standard substance high performance liquid chromatography.The high performance liquid chromatography result of the Avrmectin product that Fig. 2 embodiment 1 extracts from biochemical wastes.Ordinate zou is voltage (mv), and X-coordinate is time (min).
Embodiment
The present invention will be further described below in conjunction with drawings and Examples, but be not limited thereto.
Biochemical wastes used in the present embodiment is that the said firm produces the waste liquid that produces in the production process of L-glutamic acid available from west, Shandong king group company.The production of the said firm's L-glutamic acid is that carbon source, liquefied ammonia are the fermentation of nitrogenous source with rough glucose, reclaims remaining liquefied ammonia (formation sulfate of ammoniac) behind the broth extraction L-glutamic acid again, extracts the later residue of ammonium sulfate promptly as liquid waste disposal.This waste liquid contains the Avrmectin of 0.1-0.2%, and 50% dry-matter, 20% amino acid, 3-4% reducing sugar and 5-6% inorganic nitrogen etc.
Instrument and reagent: thermostat water bath, high performance liquid chromatography, C
18Post, separating funnel, B.The Avrmectin standard substance, acetone, methyl alcohol (chromatographically pure), acetonitrile (chromatographically pure), methylene dichloride, NaCl etc.Except that specifying that reagent is analytical pure.
Chromatographic condition: C
18Post; Moving phase: methanol-water (volume ratio 9: 1); Flow velocity: 1mL/min; Column temperature: room temperature (25 ℃).Detect wavelength: 245nm.
The preparation of standard substance: accurately take by weighing Avrmectin standard substance 50.00mg, place the 100mL volumetric flask, methyl alcohol ultra-sonic oscillation dissolving constant volume, it is standby to place refrigerator to keep in Dark Place.
Utilize biochemical wastes to extract the method for preparing Avrmectin, step is as follows:
Take by weighing the biochemical residue 20g of west, Shandong king group company, add 50ml methyl alcohol,, extract repeatedly 2 times, merge alcohol extract, use the B suction filtration with ultrasonic oscillation extraction 30min.Filtrate is gone in the separating funnel, add 100ml 10%NaCl, use dichloromethane extraction three times, combining extraction liquid.With dichloromethane extraction liquid through anhydrous Na
2SO
4Drying is filtered and is closed in the 250ml round-bottomed bottle.40 ℃ are concentrated near doing.Get the Avrmectin product.
Measure: with 10ml dissolve with methanol the said products and constant volume.Under above-mentioned chromatographic condition, treat instrument stabilizer after, inject the 20ul sample solution, measurement result.
Experimental result
Fig. 1 has shown the high performance liquid chromatography result of Avrmectin standard substance.As seen the retention time of Avrmectin is 5.8min.Wang Shenghua residue high performance liquid chromatography result such as Fig. 2 after the methylene dichloride extracting in west shows.Can find in 5-8min, to have the existence at tangible Avrmectin peak.Can illustrate and contain Avrmectin at residue.
The required equipment of method of the present invention only has agitator, plate and frame filter and heat drying equipment, so can be widely used in suitability for industrialized production.Through predesigne extract used artificial, the electricity charge of 1kg Avrmectin, starting material are approximately 550 yuan, add overheads, depreciation of equipment, the cost that extracts the 1kg Avrmectin is no more than 600 yuan, the market price of Avrmectin is 850 yuan/kg. produces 1200 ton 0.5% Avrmectin per year with company scale calculating at present, if directly buying its expense of the former medicine of Avrmectin is 5,100,000 yuan, and use its expense of Avrmectin of from biochemical residue, extracting only to need 3,600,000 yuan (western Wang Jituan), the therefore annual cost that can save 1,500,000 yuan.After applying, have higher society and ecological benefits.
Waste liquid after embodiment 1 step (3) dichloromethane extraction also can be in order to produce 10% amino acid foliage fertilizer.Concrete operations are: the waste water utilization ion exchange technique after the dichloromethane extraction recycles the heavy metal in the citric acid removal waste liquid, adds a certain amount of trace element and water again and makes 10% amino acid foliage fertilizer.
Claims (4)
1. one kind is utilized biochemical wastes to extract the method for preparing Avrmectin, comprise ethanol-extracted, filtration, extraction, described biochemical wastes is to be that carbon source, liquefied ammonia are that nitrogenous source ferments with rough glucose, remaining liquefied ammonia reclaims and forms the later waste liquid of ammonium sulfate in the fermented liquid behind the extraction L-glutamic acid, and concrete steps are as follows:
(1) add methyl alcohol in biochemical wastes, fully mixed the extraction separated and kept the upper strata extracting solution, adds methyl alcohol again in lower floor's thing, and same repeatedly operation is extracted 2-3 time, merges alcohol extract; Wherein, biochemical wastes with the ratio of methyl alcohol is: (20-40) g: (50-100) ml,
(2) alcohol extract with step (1) gained filters,
(3) the 10%NaCl solution of adding 100-150ml in the filtrate of step (2) is used dichloromethane extraction 2-3 time, combining extraction liquid, and waste liquid is recycling,
(4) with dichloromethane extraction liquid through anhydrous Na
2SO
4Drying is filtered, and 38-45 ℃ concentrates, and gets the Avrmectin product.
2. the biochemical wastes that utilizes as claimed in claim 1 extracts the method for preparing Avrmectin, it is characterized in that, fully mixed extraction of step (1) is to adopt ultrasonic oscillation extraction 30-40min, perhaps stirs and extracts 30-60min.
3. the biochemical wastes that utilizes as claimed in claim 1 extracts the method for preparing Avrmectin, it is characterized in that, the filtration of step (2) selects for use the plate and frame filter to filter or the B suction filtration.
4. the method for utilizing biochemical wastes to extract prepare Avrmectin as claimed in claim 1 is characterized in that, step (3) dichloromethane extraction waste liquid afterwards is in order to produce 10% amino acid foliage fertilizer.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100164006A CN101284857A (en) | 2008-05-28 | 2008-05-28 | Process for abstracting biological pesticide avermectin from biochemical wastes |
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| CNA2008100164006A CN101284857A (en) | 2008-05-28 | 2008-05-28 | Process for abstracting biological pesticide avermectin from biochemical wastes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489043A (en) * | 2011-12-20 | 2012-06-13 | 湖南国发精细化工科技有限公司 | Recovery technology of methylamino avermectin benzoate amination solvent |
| CN102993252A (en) * | 2012-12-31 | 2013-03-27 | 齐鲁制药（内蒙古）有限公司 | Method and device for extracting avermectins |
-
2008
- 2008-05-28 CN CNA2008100164006A patent/CN101284857A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489043A (en) * | 2011-12-20 | 2012-06-13 | 湖南国发精细化工科技有限公司 | Recovery technology of methylamino avermectin benzoate amination solvent |
| CN102489043B (en) * | 2011-12-20 | 2013-07-31 | 湖南国发精细化工科技有限公司 | Recovery technology of methylamino avermectin benzoate amination solvent |
| CN102993252A (en) * | 2012-12-31 | 2013-03-27 | 齐鲁制药（内蒙古）有限公司 | Method and device for extracting avermectins |
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Open date: 20081015 |