CN106818752B - A kind of preparation method of high-content kasugarnycin aqua - Google Patents

A kind of preparation method of high-content kasugarnycin aqua Download PDF

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CN106818752B
CN106818752B CN201611215666.4A CN201611215666A CN106818752B CN 106818752 B CN106818752 B CN 106818752B CN 201611215666 A CN201611215666 A CN 201611215666A CN 106818752 B CN106818752 B CN 106818752B
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kasugarnycin
preparation
content
aqua
preservative
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CN106818752A (en
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王震
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Shaanxi Lvdun Biopharmaceutical Innovation Center Co.,Ltd.
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C07H1/08—Separation; Purification from natural products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/20—Carbocyclic rings
    • C07H15/207—Cyclohexane rings not substituted by nitrogen atoms, e.g. kasugamycins

Abstract

The present invention relates to a kind of preparation methods of high-content kasugarnycin aqua, this method can manufacture high concentration kasugarnycin aqua of the content between 5-8%, and salinity is extremely low in product, and using effect is good and easy to use, it is able to satisfy and flies anti-grade to the demanding use demand of concentration, it is low to store freight.

Description

A kind of preparation method of high-content kasugarnycin aqua
Technical field
The invention belongs to pesticide fields, and in particular to a kind of preparation method of high-content kasugarnycin aqua.
Background technique
Kasugarnycin is a kind of aminoglycoside microbial source biological bactericide pesticide, and product is generally with one water of kasugarnycin Hydrochloride hydrate form exists, and is mainly used for preventing and treating fungies and the bacteriums such as rice blast, graw mold of tomato, citrus bacterial canker disease Venereal disease evil.Since control efficiency is preferable, kasugarnycin is using more and more extensive.
It is well known that aqua is the best dosage form of kasugarnycin, have the characteristics that environmentally friendly, efficient, safe.But existing market The kasugarnycin aqua content of upper registration is generally relatively low, and between 2% ~ 4%, transportation cost is high, inconvenient to use, is less able to satisfy What is be surging forward flies anti-etc. needs；Many product impurity contents are high, and especially salt content is high, causes product materialization Character and using effect are unstable, or even generate phytotoxicity.Therefore in the long run, these problems and defect can all influence product It promotes the use of.
There are many enterprise of domestic registration and sale kasugarnycin low content aqua at present, and major product has two classes, Yi Leishi It has passed through a degree of purification, but content is not high, generally in 2-4%；Another kind of is not purified thick aqua, only will Fermentation liquid is concentrated to 2%.These two types of product common problems are exactly impurity content height, and the impurity such as salinity and harmful ion do not have There is control, physicochemical properties are unstable, and using effect is bad, or even can generate phytotoxicity.
In terms of the development of kasugarnycin, the patent having disclosed has very much, and the report in terms of purification mainly has mountain " a kind of extraction process of kasugarnycin aqua " (201510196286.X) disclosed in Xi Xinyuanhua health chemical inc, The method of purification of 0.5%-4% kasugarnycin solution has been sketched in the patent.Aspect that there are three the existing main deficiencies of this report, It is desorbed one is using saturated ammonium chloride, a large amount of ammonium salts is caused to remain in stripping liquid, finally take off ammonium with nanofiltration, nanofiltration membrane is negative Lotus is high, it is difficult to thoroughly remove ammonium salt, last a large amount of ammonium salts remain in the solution, into product.It is molten referring to ammonium chloride according to applicant Angle value actual measurement is solved, at 20 DEG C, the solubility of industrial ammonium chloride is more than 30g, that is, the ammonium chloride percentage composition of solution is more than 23%, in addition to small part is exchanged on resin, largely stay in the product, and nanofiltration is applied alone to take off ammonium, industrially it is difficult to realize this Function also demonstrates this point in applicant's long-term practice.Second, since salt residues ammonium chloride content is high, product spring thunder Mycin content is difficult to improve, can only be between 0.5-4%.Third, nanofiltration can only slough monovalent ion, for bringing into fermentation liquid The divalent ions such as calcium, magnesium, can only stay in the product, form impurity, influence product content and further increase.
Summary of the invention
In order to overcome problems of the prior art, the present invention provides a kind of preparation side of high-content kasugarnycin aqua Method, this method can manufacture high concentration kasugarnycin aqua of the content between 5-8%, and salinity is extremely low in product, and using effect is good And it is easy to use, it is able to satisfy and flies anti-grade to the demanding use demand of concentration, it is low to store freight.
The present invention adopts the following technical scheme: a kind of preparation method of high-content kasugarnycin aqua, comprising the following steps:
(1) the fermentation liquid pH value of kasugarnycin is adjusted between 2 and 6, removes the Ca in fermentation liquid2 +、 Mg2+；
(2) ultrafiltration membrance filter is used, gained filtrate uses styrene-divinylbenzene crosslinking copolymerization structure highly acidic cation Exchanger resin adsorption of effective component, sloughs impurity；
(3) it is solved using the sodium hydroxide solution of 0.05mol/L(0.02%) to 0.5mol/L (2%) as parsing agent Analysis, obtains desorbed solution, 5 ~ 40m/h of elution flow rate；Overwhelming majority Na during elution+It is switched on resin, reduces salt Divide and brings product into；
(4) pH of obtained desorbed solution is adjusted to 1.5 ~ 6, is concentrated using nanofiltration, circulating filtration removes residue Na+Salt； After nanofiltration repeatedly, control kasugarnycin content and solid content is met the requirements, it is diluted to required concentration with pure water, preservative is added, Required kasugarnycin aqua is made.
In a preferred embodiment of the present invention, the fermentation liquid of the kasugarnycin is to be produced using actinomycete fermentation The fermentation liquid of kasugarnycin.
In a preferred embodiment of the present invention, using careless acid for adjusting pH value in step (1), pH value is preferably 3.5.
In a preferred embodiment of the present invention, the preferably 734 sodium form resins of resin described in step (2), adsorption flow rate For 5 ~ 40m/h, preferably 20 m/h.
In a preferred embodiment of the present invention, use 0.15mol/L (0.6%) in step (3)) sodium hydroxide solution It is parsed as parsing agent, elution flow rate is 18 m/h.
In a preferred embodiment of the present invention, hydrochloric acid is used in step (4) to adjust the pH value of desorbed solution as 3.5, with Remove NaOH extra in desorbed solution.
In a preferred embodiment of the present invention, 2nm is less than using aperture in step (4), retains organic matter molecular mass The nanofiltration membrane dehydration of 150-300, which is concentrated, simultaneously removes NaCl, when nanofiltration membrane permeate speed is reduced to normal speed 40%, to dense Addition is with permeate equal quality in contracting liquid and conductivity is less than 10 μ S/cm pure water, continues concentrating and desalinating, repeatedly until spring thunder is mould Cellulose content is greater than 8.5%, and solid content is less than 10.6% and NaCl content is less than 0.05%.
In a preferred embodiment of the present invention, pure water described in step (4) is pure water of the conductivity less than 20 μ S/cm.
In a preferred embodiment of the present invention, the preservative be benzoic acid and its esters, sorbic acid and its esters, One of propionic acid and its esters, p-hydroxybenzoate, quaternary ammonium salt are a variety of；Preferably sodium benzoate, it is cheap suitable With；The dosage of the preservative be 0.1%-0.5%, preferably 0.3%.
In a preferred embodiment of the present invention, the kasugarnycin aqua after preservative is added needs to adjust pH to 1.5- 3.5。
In a preferred embodiment of the present invention, the kasugarnycin aqua after preservative is added is needed with 10mol/L hydrochloric acid (aqua stoste) pH is adjusted to 2.8.
Compared with prior art, the present invention has the following technical effect that:
(1) a kind of preparation method of aqua more higher than kasugarnycin content in existing product is provided, can manufacture and contain The high concentration kasugarnycin aqua between 5-8% is measured, removing impurities matter is thorough, and product purification efficiency is high, and salt content is low in aqua, especially The features such as it is that NaCl content is low, and using effect is good, and character is stablized.
(2) mould using styrene-divinylbenzene crosslinking copolymerization structure sodium form storng-acid cation exchange resin absorption spring thunder Element avoids introducing high salt concentration using the NaOH of low concentration as eluant, eluent, this is also a pass for preparing high-content aqua Key.
(3) concentrating and desalinating repeatedly in nanofiltration concentration process controls NaCl content below 0.05%.
(4) pass through repetition test, concentration liquid hold-up is 8.5% or more, and solid content is below 10.6% and NaCl content When less than 0.05%, concentrate can be configured to the stable aqua of character, meet aqueous pesticide solution requirement.This is also to prepare high-content water Another of agent is crucial.
Specific embodiment
In order to keep the purpose of the present invention, technical solution and beneficial effect clearer, present invention following specific embodiments It is illustrated, but the present invention is limited to absolutely not these examples.
Embodiment 1:
(1) weighing content is 1.50% fermentation liquid 2500Kg, and with careless acid for adjusting pH=3.5, ultra-filtration filters are total to filter out 3800Kg filtered fluid, mixed liquor detection level are 0.94%.
(2) 3800Kg filtrate is passed through into 734 sodium form resins with the speed of 20m/h, sloughs impurity.
(3) it is eluted with 0.15mol/LNaOH with the speed of 18m/h, obtaining content is 3.42% kasugarnycin solution 996Kg, pH=7.4.
(4) pH is adjusted to 3.5 with 0.15mol hydrochloric acid, using 1 nanometer of aperture, molecular cut off is that 150-300 nanofiltration is dense Contracting, when being concentrated into 502Kg, flow velocity is reduced to the 40% of threshold speed, and 9.1 μ S/cm pure water 494Kg of conductivity is added and continues to be concentrated, Repeatedly three times, through detecting, content 8.53%, solid content 10.59%, NaCl content 0.047%, shut down, obtain concentrate 385Kg。
It takes concentrate 150Kg, 0.48Kg sodium benzoate is added, 8.58Kg conductivity is added less than 9.1 μ S/cm pure water, 10mol/L concentrated hydrochloric acid 0.5Kg is added, obtains 8% kasugarnycin aqua 159.56Kg, medical fluid pH2.8.The 150Kg concentrate is taken, 0.64Kg sodium benzoate is added, 62.00Kg conductivity is added less than 9.1 μ S/cm pure water, 0.61Kg10mol/L concentrated hydrochloric acid is added, Obtain 6% kasugarnycin aqua 213.25Kg, medical fluid pH2.8.Concentrate 85Kg is taken, 0.44Kg sodium benzoate is added, is added 59.17Kg conductivity is added 0.4Kg10mol/L concentrated hydrochloric acid, obtains 5% kasugarnycin aqua less than 9.1 μ S/cm pure water 145.01Kg medical fluid pH2.8.
Embodiment 2:
(1) weighing content is 1.03% fermentation liquid 2500Kg, and with careless acid for adjusting pH=3.5, ultra-filtration filters are total to filter out 3805Kg filtered fluid, mixed liquor detection level are 0.65%.
(2) 3805Kg filtrate is passed through into 734 sodium form resins with the speed of 20m/h, sloughs impurity.
(3) it is eluted with 0.15mol/LNaOH with the speed of 18m/h, obtaining content is 3.36% kasugarnycin solution 700Kg, pH=7.4.
(3) pH is adjusted to 3.5 with 0.15mol hydrochloric acid, using 1 nanometer of aperture, molecular cut off is 150-300 nanofiltration membrane Concentration, when being concentrated into 502Kg, flow velocity is reduced to the 40% of threshold speed, be added conductivity less than 9.8 μ S/cm pure water 494Kg after Continuous concentration, repeatedly three times, through detecting, content 8.50%, solid content 10.55%, NaCl content 0.047% shuts down, obtains To concentrate 274Kg.
1.00Kg sodium benzoate is added into the concentrate, 56.41Kg conductivity is added less than 9.8 μ S/cm pure water, is added 1.3Kg10mol/L concentrated hydrochloric acid obtains 7% kasugarnycin aqua 332.71Kg, medical fluid pH2.8.
Although invention has been described by referring to the preferred embodiment of the present invention, this field it is common It will be appreciated by the skilled person that various changes can be made to it in the form and details, without departing from appended right The spirit and scope of the present invention defined by claim.

Claims (10)

1. a kind of preparation method of high-content kasugarnycin aqua, which comprises the following steps:
(1) pH value of the fermentation liquid of kasugarnycin is adjusted between 2 and 6, removes the Ca in fermentation liquid2 +、 Mg2+；
(2) ultrafiltration membrance filter is used, gained filtrate is exchanged using styrene-divinylbenzene crosslinking copolymerization structure highly acidic cation Resin adsorption effective component, sloughs impurity, and adsorption flow rate is 5 ~ 40m/h；
(3) it is parsed using the sodium hydroxide solution of 0.05mol/L to 0.5mol/L as parsing agent, obtains desorbed solution, wash 5 ~ 40m/h of separation of flow speed；
(4) pH of obtained desorbed solution is adjusted to 1.5 ~ 6, is concentrated using nanofiltration, circulating filtration removes residue Na+Salt；It receives repeatedly After filter, control kasugarnycin content and solid content are met the requirements, it is diluted to required concentration with pure water, preservative is added, institute is made Need kasugarnycin aqua；
2nm is less than using aperture in step (4), the nanofiltration membrane dehydration of retention organic matter molecular mass 150-300 is concentrated and removes NaCl, when nanofiltration membrane permeate speed is reduced to normal speed 40%, addition and permeate equal quality and electricity into concentrate Conductance continues concentrating and desalinating less than 10 μ S/cm pure water, and repeatedly until kasugarnycin content is greater than 8.5%, solid content is less than 10.6% and NaCl content is less than 0.05%.
2. preparation method according to claim 1, which is characterized in that the fermentation liquid of the kasugarnycin is using unwrapping wire The fermentation liquid of the kasugarnycin of bacterium fermenting and producing.
3. preparation method according to claim 1, which is characterized in that using careless acid for adjusting pH value in step (1), pH value is 3.5。
4. preparation method according to claim 1, which is characterized in that resin described in step (2) is 734 sodium form trees Rouge, adsorption flow rate are 20 m/h.
5. preparation method according to claim 1, which is characterized in that using the hydrogen of 0.15mol/L (0.6%) in step (3) Sodium hydroxide solution is parsed as parsing agent, and elution flow rate is 18 m/h.
6. preparation method according to claim 1, which is characterized in that adjust desorbed solution using hydrochloric acid in step (4) PH value is 3.5, to remove NaOH extra in desorbed solution.
7. preparation method according to claim 1, which is characterized in that pure water described in step (4) is conductivity less than 20 μ The pure water of S/cm.
8. preparation method according to claim 1, which is characterized in that the preservative is benzoic acid and its esters, mountain Pears acid and one of its esters, propionic acid and its esters, p-hydroxybenzoate, quaternary ammonium salt or a variety of；The preservative Dosage be 0.1%-0.5%.
9. preparation method according to claim 1, which is characterized in that the kasugarnycin aqua after preservative is added needs to adjust Whole pH to 1.5-3.5.
10. preparation method according to claim 1, which is characterized in that the preservative is sodium benzoate；Described is anti- The dosage of rotten agent is 0.3%；Kasugarnycin aqua after preservative is added needs to adjust pH to 2.8.
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107549164A (en) * 2017-08-28 2018-01-09 江苏绿叶农化有限公司 A kind of preparation method of kasugarnycin aqua
CN109666051B (en) * 2017-10-17 2021-10-29 福州奥尼多生物科技有限公司 Purification method of kasugamycin
CN107987110A (en) * 2017-12-15 2018-05-04 陕西麦可罗生物科技有限公司 A kind of desalination process of kasugarnycin concentrate
CN110452275B (en) * 2019-09-17 2023-04-07 陕西绿盾环境工程研究院有限公司 Preparation method of high-purity kasugamycin
CN110743630A (en) * 2019-11-14 2020-02-04 江门市植保有限公司 Ion exchange equipment for preparing kasugamycin aqueous solution and aqueous solution preparation method
CN112205409A (en) * 2020-11-27 2021-01-12 陕西麦可罗生物科技有限公司 Kasugamycin and Xinjunan compound water aqua and preparation method thereof
CN113563397B (en) * 2021-09-01 2023-07-04 山东良福制药有限公司 Abelica star purification method
CN114230622A (en) * 2021-11-12 2022-03-25 陕西麦可罗生物科技有限公司 Method for decoloring kasugamycin concentrated solution
CN117063933B (en) * 2023-10-16 2023-12-26 中国远大集团有限责任公司 Kasugamycin organic acid salt, pesticide composition containing kasugamycin organic acid salt and application of kasugamycin organic acid salt

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CN102250165A (en) * 2011-06-03 2011-11-23 陕西绿盾生物制品有限责任公司 Preparation method of technical grade kasumin
CN104770369A (en) * 2015-04-23 2015-07-15 山西新源华康化工股份有限公司 Kasugamycin water-aqua extracting process

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102250165A (en) * 2011-06-03 2011-11-23 陕西绿盾生物制品有限责任公司 Preparation method of technical grade kasumin
CN104770369A (en) * 2015-04-23 2015-07-15 山西新源华康化工股份有限公司 Kasugamycin water-aqua extracting process

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Effective date of registration: 20221116

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Patentee before: Wang Zhen