CN108503046A - A kind of organic pollution complex microorganism degradation agent and preparation method - Google Patents

A kind of organic pollution complex microorganism degradation agent and preparation method Download PDF

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Publication number
CN108503046A
CN108503046A CN201810340445.2A CN201810340445A CN108503046A CN 108503046 A CN108503046 A CN 108503046A CN 201810340445 A CN201810340445 A CN 201810340445A CN 108503046 A CN108503046 A CN 108503046A
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organic pollution
complex microorganism
titanium dioxide
degradation
powder
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李锦成
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Foshan Shang Bai Science And Technology Co Ltd
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Foshan Shang Bai Science And Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The present invention relates to field of environment protection, are related to the degradation of biomaterial and/or catalysis material to organic waste materials.Wherein microbial strains are selected from one or more in bacillus subtilis (Bacillus subtilis), bacillus megaterium (Bacillus megaterium), aspergillus sydowii (Aspergillus sydowii), wherein the preferred preserving number of bacillus subtilis is the bacillus subtilis of CGMCC NO.1.9083, and the preferred preserving number of bacillus megaterium is the bacillus megaterium of CGMCC NO.1.16094；The preferred preserving number of aspergillus sydowii be CGMCC NO.3.13937, coordinated with mentioned microorganism using photochemical catalyst nano-titanium dioxide, degrading pesticide, especially degrading methamidophos, parathion-methyl, Hostathion application on, achieve extraordinary effect.

Description

A kind of organic pollution complex microorganism degradation agent and preparation method
Technical field
The present invention relates to field of environment protection, and in particular to the processing of the organic pollution (such as pesticide, chemical industry waste) in environment, Degradation further to biomaterial and/or catalysis material to organic waste materials.
Background technology
With the high speed development of industrialization degree, all inevitably will produce in industry or agricultural production process a large amount of discarded Object, for example, the organic waste of chemical plant discharge, farmland pesticide residue and pesticide in water body is finally flowed into rainwater etc.. As we pay attention to the understanding of environmental protection and gradually, the processing of above-mentioned pollutant becomes particularly important.
Chemical pesticide is artificial synthesized biological exogenous material, many pesticides be to the mankind or other biologies it is toxic, And the pesticide residue of many types is more difficult to degrade.This keeps pesticide excessively serious negative using producing in the production of agricultural It influences, the physical and mental health for injuring and threaten the mankind is brought to non-target organism, so, reinforce degradation of pesticide research, solve pesticide Pollution problem to environment and food is current one of the project in the urgent need to address of the mankind.These pesticide residues are widely distributed In soil, water body, in air and agricultural product, but be mainly distributed across in soil and water body.In fact, pesticide residue is certainly Right boundary relies primarily on microorganism and slowly degrades, although this is by elements, does not generate the ideal of secondary pollution on the way Diameter.But its degradation speed cannot be satisfied the requirement of environmental protection.In recent years with the attention to pesticide residual contamination problem, scientist A large amount of research carried out to pesticide biodegradation, but many problems still have it is to be solved.
It is now many currently used for the approach of degradation of pesticide.Such as it is degraded to pesticide residue using microorganism.In soil Bacterium, fungi, all there are some types in actinomyces and algae and have the function of degradation of pesticide, bacterium is due to more on its biochemistry Kind adaptability and easy Mutation induction bacterial strain, occupy main status in degradation of pesticide.Usually, in soil, sewage and height In warm composting system, decompose that play a major role is bacterium class to pesticide, this and pesticide type, the ability of Degradation of Pesticides By Microorganisms It is related with environmental condition etc..By the effect of microorganism, the organic pollution in environment is converted into CO2And H2O etc. is nontoxic Or the other materials that toxicity is smaller.Such as patent CN102755991 relates to repair organophosphor using organophosphorus pesticide degradation bacterium Pesticide contaminated soil；Patent CN104371594 is directed to a kind of bacillus of the degradation applied to pedo relict pesticide (Bacillus Sp.)FZUL-33.The shortcomings that microbial degradation, is that the pesticide variety range of microbial degradation is often relatively narrow, very Difficulty finds the microbe species with wide spectrum degrading activity；Second, the application environment of microorganism is also subject to many limitations, because needing Ensure the physiological activity of microorganism；The degradation rate of third, microorganism is also irregular, and the degradation rate of many microorganisms is all It cannot meet the needs.
The mode of another degradable organic pollutant or chemical pesticide is to utilize photocatalytic degradation, it is degraded under normal conditions Speed can be more rapid for biodegradation, the type of degradation is more, can make up microbial degradation it is many not Foot.It includes nano-titanium dioxide (N-TiO wherein to study more2), four-needle-like zinc oxide (T-ZnOw), nano zine oxide (N- ZnO) etc..Such as patent CN103081735, it relates to degrade to pesticide using nano-titanium dioxide.But it is urged using light Changing degradation also has its existing shortcomings：It is that its application environment is limited first, photochemical catalyst will play degradation, usually need Photocatalysis is played, electron hole is generated by ultraviolet light or radiation of visible light, and then generate with strong reactivity Free radical.Therefore, in the soil or compared in dark situation, the use of photochemical catalyst just receives limitation.Second, photochemical catalyst Use cost is also relatively high, and show certainly has first had numerous studies to be dedicated to recyclable photochemical catalyst research at present, It is main to be to confer to photochemical catalyst magnetism.
Invention content
Present invention discover that the above-mentioned problems in the prior art, is expected that by microbial degradation material and photocatalysis drop Solution material mating is used or is applied in combination, to obtain better degradation effect.But this compounding is not simply by two Kind combination of materials uses, it is also necessary to overcome more difficulty.Known difficulty includes：Catalysis material is certain by all having Bactericidal activity, therefore in the case that it is compounded with microorganism, be easy to have an impact the physiological activity of microorganism, therefore screen Suitable microbe species and protective agent appropriate seem that comparison is crucial.
An aspect of of the present present invention provides a kind of organic pollution complex microorganism degradation agent, wherein comprising having degradation work( The bacterium powder of the microbial strains of energy, catalysis material, protective agent, and other optional as needed auxiliary materials.With raw material Total weight, the percentage composition of each component is：The bacterium powder 1%-20% of microbial strains, catalysis material 10-60%, protection Agent 10-20%, other auxiliary materials 20%-60%.Wherein bacterium powder contains viable bacteria or spore amount needs to be more than 0.5 hundred million cfu/g, Preferably hundred million cfu/g of 1-5.
Wherein microbial strains are selected from bacillus subtilis (Bacillus subtilis), bacillus megaterium It is one or more in (Bacillus megaterium), aspergillus sydowii (Aspergillus sydowii), wherein withered grass bud The preferred preserving number of spore bacillus is the bacillus subtilis of CGMCC NO.1.9083, and the preferred preserving number of bacillus megaterium is CGMCC The bacillus megaterium of NO.1.16094；The preferred preserving number of aspergillus sydowii is CGMCC NO.3.13937.
The microbial material related in the present invention passes through China General Microbiological culture presevation administrative center (China General Microbiological Culture Collection Center, CGMCC) is commercially available.
The wherein described catalysis material can be selected from nano-titanium dioxide (N-TiO2), four-needle-like zinc oxide (T-ZnOw), receive It is one or more in rice zinc oxide (N-ZnO), it is chosen in particular from (N-TiO2)。
The protective agent is mainly used for protecting the substance of thalline, preferably vegetable oil and butylated hydroxy anisole (BHA), Wherein vegetable oil main function is that thalline is being allowed to infiltrate, and also functions to certain buffer action, therefore select known in the art one As vegetable oil, preferred grape seed oil, the two weight proportion is BHA：Vegetable oil is 1:5-20.
Other described auxiliary materials include one or more in carrier, wetting agent, dispersant, adhesive, solvent.Wherein carry Body can be the common carrier of this field, specifically, such as：Glucose, maltose, sucrose, white carbon, kaolin, diatomite, It is float stone, dextrin, cellulose powder, precipitated calcium carbonate, organobentonite, clay, talcum, soluble starch, Anhydrous potassium carbonate, anhydrous The mixture and natrium carbonicum calcinatum of sodium carbonate, Carbon Dioxide hydrogen potassium, anhydrous sodium bicarbonate, Anhydrous potassium carbonate and Carbon Dioxide hydrogen potassium With it is one or more in the mixture of anhydrous sodium bicarbonate.
The wetting agent can be the various wetting agents of this field, and specifically, which can be dodecyl sulphate Sodium, Teepol, neopelex, fatty alcohol polyglycol ether sulfate and alkylnaphthalene sulfonate and anion It is one or more in the mixture of wetting agent.
The dispersant can be the various dispersants of this field, and specifically, which is polycarboxylate salt dispersant, gathers Sodium acrylate, alkylnaphthalene sulfonate, sodium methylene bis-naphthalene sulfonate, lignosulfonates, alkamide taurine salt, naphthalene sulfonic acids It is one or more in salt, the sodium salt of alkyl naphthalene sulfonic acid condensation polymer and alkyl naphthalene sulfonic acid yuban.
Described adhesive can be the various adhesives of this field, and specifically, which is carboxymethyl cellulose, β-ring It is one or more in dextrin, xanthans, trehalose.
The solvent can be the common solvent of this field, and specifically, which can be organic solvent, vegetable oil, mine It is one or more in object oil, solvent naphtha and water.Wherein, the organic solvent includes N-Methyl pyrrolidone, tetrahydrofuran, two Methyl sulfoxide, spectrasolv DMDA, n,N-Dimethylformamide, dimethylbenzene, tetrahydrofurfuryl alcohol, tributyl phosphate, Isosorbide-5-Nitrae-two It is one or more in six ring of oxygen and cyclohexanone.The vegetable oil includes epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor It is one or more in sesame oil, corn oil and pine-seed oil.The mineral oil includes one in liquid wax, machine oil, kerosene and lubricating oil Kind is a variety of.The solvent naphtha includes one or more in No. 100 solvent naphthas, No. 150 solvent naphthas and No. 200 solvent naphthas.
Another aspect of the present invention further relates to the preparation method of above-mentioned organic pollution complex microorganism degradation agent, including with Lower step：
1) nano-titanium dioxide powder is configured, sol-gal process is used to prepare grain size as the nanometer two within the scope of 1-100nm Titanium oxide；
2) bacterial strain is cultivated, the fermentate of bacterial strain is obtained, bacterium powder is obtained by dry；
3) bacterium powder, vegetable oil and butylated hydroxy anisole (BHA) are weighed according to parts by weight, it is slowly mixed in blender Close uniform treated bacterium powder；
4) other auxiliary materials are mixed, obtains agent mixture；
5) nano-titanium dioxide that step 1) is prepared is mixed by weight ratio with bacterium powder, adds auxiliary agent mixing Object stirs evenly in blender, drying, screening, packaging, obtains the organic pollution complex microorganism degradation Agent.
Wherein step 1) prepares the nano-titanium dioxide that nano-titanium dioxide has been highly developed using sol-gal process Arbitrary sol-gal process may be used to prepare in technology of preparing, those skilled in the art.It is specifically as follows：It first will be a certain amount of Water and ethyl alcohol by volume 1:4 mixing, and acid or alkali adjusting pH value of solution is added, solution is obtained as reaction medium, then will A certain amount of presoma tetra-n-butyl titanate (TBT) mixes with ethyl alcohol, and as precursors, water and second are added drop-wise at 75 DEG C The in the mixed solvent of alcohol, and continue to react at 75 DEG C for 24 hours after being added dropwise, obtained suspension is subjected to high speed centrifugation, It is washed with water and ethyl alcohol, nano titanium dioxide powder is obtained after dry.
Wherein step 2), bacterium powder therein include thalline powder, also contemplated conidia powder, can be seen as bacterium powder.This field Technical staff can select suitable training method according to the bacterial strain of specific choice, and culture herein is used for the purpose of being expanded The thalline of exhibition, and the technical staff that the training method of bacillus and aspergillus sydowii should be microorganism field is known, It should not be taken as the limitation that effect of the present invention is realized.Adoptable preparation method is as follows：
The preparation of bacterium bacterium powder/conidia powder：The original strain of bacillus is aseptically carried out to inclined-plane training successively It supports, after shaking table culture, fermentation tank culture, obtained zymotic fluid is prepared into bacterial spore powder by concentrate drying；
The preparation of aspergillus sydowii conidia powder：By aspergillus sydowii original strain aseptically successively carry out inclined-plane culture, After shaking table culture, fermentation tank culture, solid fermentation production spore, the culture medium of obtained complete production spore is soaked respectively and is made in clear water Then obtained aspergillus sydowii spore suspension is concentrated and dried by spore suspension to obtain aspergillus sydowii spore suspension It is prepared into aspergillus sydowii conidia powder；
Specific implementation mode
Embodiment 1 prepares nano-titanium dioxide
First by the water of 30mL and 120mL ethyl alcohol by volume 1:4 mixing, and acid or alkali adjusting pH value of solution is added, it obtains Then solution mixes the presoma tetra-n-butyl titanate (TBT) of 18mL with ethyl alcohol, as reaction medium as reaction precursor Body is added drop-wise to the in the mixed solvent of water and ethyl alcohol at 75 DEG C, and continues to react at 75 DEG C for 24 hours after being added dropwise, will The suspension arrived carries out high speed centrifugation, is washed with water and ethyl alcohol, and nano titanium dioxide powder is obtained after dry.
Embodiment 2 prepares bacterium powder
1, bacillus bacterium powder is prepared
A. inclined-plane culture：Bacillus subtilis, bacillus megaterium original strain are aseptically inoculated in respectively On slant medium, cultivated 24~36 hours under the conditions of 30 ± 2 DEG C；
B. shaking table culture：The strain that step a is cultivated aseptically is inoculated in seed culture medium respectively, PH7.0~7.5, under the conditions of 30 DEG C, 160~180r/min shaking table cultures 12~18 hours；
C. fermentation tank culture：The strain that step b is cultivated aseptically is inoculated in liquid fermentation medium respectively, 0.5kg/cm is pressed in pH7.0~8.0, tank2, 30 DEG C, ventilation quantity 1:Under the conditions of 0.8~1.1, after cultivating 48~72 hours, 80% Thalline becomes gemma tank at present, obtains zymotic fluid；
D. by the zymotic fluid obtained in step c it is concentrated after, be prepared by proper proportion and carrier rice husk powder combination drying Each bacterial spore powder；
2, aspergillus sydowii conidia powder is prepared
A. aspergillus sydowii original strain is aseptically inoculated on slant medium, 72 is cultivated under the conditions of 28 DEG C Hour；
B. shaking table culture：The strain that step a is cultivated aseptically is inoculated in seed culture medium, pH6.5~ 6.8, under the conditions of 30 DEG C, 150r/min shaking table cultures 72 hours；
C. fermentation tank culture：The step b strains cultivated aseptically are inoculated in liquid fermentation medium respectively, PH6.5~6.8, tank press 0.5kg/cm2, 27~28 DEG C, ventilation quantity 1:0.6~0.8, after 48 hours of incubation, mycelium accounts for Total volume 20% when terminate fermentation, carry out solid fermentation produce spore；
D. solid fermentation produces spore：Mycelium of the step c after fermentation tank culture is inoculated on solid fermentation culture medium, Culture 72~96 hours stops fermentation when aspergillus sydowii 90% produces spore；
E. the fermentation materials for producing spore in step d completely are immersed in clear water and spore suspension is made, it is poly- mostly bent to obtain Mould spore suspension；
F. conidia powder is made in the aspergillus sydowii spore suspension obtained in above-mentioned steps e concentrate drying.
By the above-mentioned bacterium powder being prepared and protective agent, (BHA is with grape seed oil by 1:10 mixing) be uniformly mixed, obtain with Bacterium powder used by lower experiment.
Embodiment 3 prepares organic pollution complex microorganism degradation agent
Bacterium powder, vegetable oil, BHA are weighed according to parts by weight, it is slowly mixed together in blender to uniform treated bacterium Powder or conidia powder；Other auxiliary materials are mixed, agent mixture is obtained；It is received by weight ratio by what embodiment 1 was prepared Rice titanium dioxide is mixed with bacterium powder, is added agent mixture, is stirred evenly in blender, drying, screening, packet Dress obtains organic pollution complex microorganism degradation agent.
Following product is specifically prepared (with weight percent characterization each component dosage)：
Product 1：Bacillus subtilis powder (preserving number is CGMCC NO.1.9083, about 100,000,000 cfu/g) 5%, nanometer two Titanium oxide 30%, BHA 1%, grape seed oil 9%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, Negel 2%, carboxymethyl cellulose 5%, surplus are water.
Product 2：Bacillus subtilis powder (preserving number is CGMCC NO.1.9083, about 100,000,000 cfu/g) 4%, nanometer two Titanium oxide 40%, BHA 1%, grape seed oil 9%, diatomite 10%, precipitated calcium carbonate 20%, fatty alcohol polyglycol ether sulfuric acid Sodium 3%, carboxymethyl cellulose 5%, surplus are water.
Product 3：Bacillus subtilis powder (preserving number is CGMCC NO.1.9083, about 100,000,000 cfu/g) 2%, nanometer two Titanium oxide 50%, BHA 1%, grape seed oil 9%, diatomite 15%, white carbon 10%, carboxymethyl cellulose 5%, surplus are Water.
Product 4：Bacillus subtilis powder (preserving number is CGMCC NO.1.9083, about 100,000,000 cfu/g) 10%, nanometer two Titanium oxide 30%, BHA 1.5%, grape seed oil 13.5%, diatomite 15%, precipitated calcium carbonate 10%, dodecyl benzene sulfonic acid Sodium 5%, beta-cyclodextrin 5%, surplus are water.
Product 5：Bacillus subtilis powder (preserving number is CGMCC NO.1.9083, about 100,000,000 cfu/g) 20%, nanometer two Titanium oxide 20%, BHA 2%, grape seed oil 18%, organobentonite 15%, soluble starch 10%, dodecyl benzene sulfonic acid Sodium 5%, surplus are water.
Product 6：Bacillus megaterium bacterium powder (preserving number is CGMCC NO.1.16094, about 100,000,000 cfu/g) 5%, nanometer two Titanium oxide 30%, BHA 1%, grape seed oil 9%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, Negel 2%, carboxymethyl cellulose 5%, surplus are water.
Product 7：Bacillus megaterium bacterium powder (preserving number is CGMCC NO.1.16094, about 100,000,000 cfu/g) 4%, nanometer two Titanium oxide 40%, BHA 1%, grape seed oil 9%, diatomite 10%, precipitated calcium carbonate 20%, fatty alcohol polyglycol ether sulfuric acid Sodium 3%, carboxymethyl cellulose 5%, surplus are water.
Product 8：Bacillus megaterium bacterium powder (preserving number is CGMCC NO.1.16094, about 100,000,000 cfu/g) 2%, nanometer two Titanium oxide 50%, BHA 1%, grape seed oil 9%, diatomite 15%, white carbon 10%, carboxymethyl cellulose 5%, surplus are Water.
Product 9：Bacillus megaterium bacterium powder (preserving number is CGMCC NO.1.16094, about 100,000,000 cfu/g) 10%, nanometer Titanium dioxide 30%, BHA 1.5%, grape seed oil 13.5%, diatomite 15%, precipitated calcium carbonate 10%, detergent alkylate sulphur Sour sodium 5%, beta-cyclodextrin 5%, surplus are water.
Product 10：Bacillus megaterium bacterium powder (preserving number is CGMCC NO.1.16094, about 100,000,000 cfu/g) 20%, nanometer Titanium dioxide 20%, BHA 2%, grape seed oil 18%, organobentonite 15%, soluble starch 10%, detergent alkylate sulphur Sour sodium 5%, surplus are water.
Product 11：Aspergillus sydowii (preserving number is CGMCC NO.3.13937, about 100,000,000 cfu/g) 5%, nano-titanium dioxide 30%, BHA 1%, grape seed oil 9%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, alkylnaphthalene Sodium sulfonate 2%, carboxymethyl cellulose 5%, surplus are water.
Product 12：Aspergillus sydowii (preserving number is CGMCC NO.3.13937, about 100,000,000 cfu/g) 4%, nano-titanium dioxide 40%, BHA 1%, grape seed oil 9%, diatomite 10%, precipitated calcium carbonate 20%, fatty alcohol polyglycol ether sodium sulphate 3%, Carboxymethyl cellulose 5%, surplus are water.
Product 13：Aspergillus sydowii (preserving number is CGMCC NO.3.13937, about 100,000,000 cfu/g) 2%, nano-titanium dioxide 50%, BHA 1%, grape seed oil 9%, diatomite 15%, white carbon 10%, carboxymethyl cellulose 5%, surplus are water.
Product 14：Aspergillus sydowii (preserving number is CGMCC NO.3.13937, about 100,000,000 cfu/g) 10%, nano-titanium dioxide 30%, BHA 1.5%, grape seed oil 13.5%, diatomite 15%, precipitated calcium carbonate 10%, neopelex 5%, Beta-cyclodextrin 5%, surplus are water.
Product 15：Aspergillus sydowii (preserving number is CGMCC NO.3.13937, about 100,000,000 cfu/g) 20%, nano-titanium dioxide 20%, BHA 2%, grape seed oil 18%, organobentonite 15%, soluble starch 10%, neopelex 5%, Surplus is water.
Comparative example 1：Bacillus subtilis powder (preserving number is CGMCC NO.1.9083, about 100,000,000 cfu/g) 10%, BHA 1%, grape seed oil 9%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, Negel 2%, carboxymethyl cellulose 5%, surplus is water.
Comparative example 2：Bacillus megaterium bacterium powder (preserving number is CGMCC NO.1.16094, about 100,000,000 cfu/g) 10%, BHA 1%, grape seed oil 9%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, Negel 2%, carboxymethyl cellulose 5%, surplus is water.
Comparative example 3：Aspergillus sydowii (preserving number is CGMCC NO.3.13937, about 100,000,000 cfu/g) 5%, BHA 10%, Portugal Grape seed oil 9%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, Negel 2%, carboxylic first Base cellulose 5%, surplus are water.
Comparative example 4：Nano-titanium dioxide 50%, glucose 15%, precipitated calcium carbonate 20%, neopelex 5%, Negel 2%, carboxymethyl cellulose 5%, surplus is water.
Test example 1
The sample list tested is as follows：
1 test example test sample of table is numbered
Test method：
Certain density pesticide dispersion system is configured, acephatemet, parathion-methyl, Hostathion preparation is weighed respectively and prepares water Dispersion liquid makes farm chemical ingredients be in evenly dispersed state, and dispersion liquid total volume is 1L, and the content of wherein pesticide active ingredient is D0=100mg/L.Glucose 2g, peptone 0.5g, yeast extract 0.5g is added into dispersion liquid again, it is former to form pesticide to be decomposed Liquid.Pesticide stoste to be decomposed is poured into the container for being provided with agitating device, air-breather.Take 1g samples that above-mentioned pesticide is added former It is appropriate to ventilate in liquid, stirring, while keeping illumination.It is sampled after 1h, 2d, 4d, 6d, detection pesticide concentration D1, meter Calculate degradation rate.Degradation rate DE=(D0-D1)/D0× 100%.
Using ASMK romasil-C18 reversed-phase columns (2.5 × 15cm) high performance liquid chromatograph (HP LC, Beckman Co. each pesticide concentration, using methanol-water as mobile phase, flow velocity 1.0mL/min, 20 μ L of sample size) are measured.
It should be noted that above-mentioned organophosphorus pesticide is first to be degraded to intermediate product first in degradation process, then into one Step degradation generates PO4 3-Equal inorganic ions；Therefore there are the modes of two kinds of characterization organic phosphorus pesticide degradation rates.One is above-mentioned The mode of literary grace, this mode are degraded to judge index with organophosphor, do not need it and are degraded to inorganic PO completely4 3-From Son.Also there is document using the PO for measuring generation in the prior art4 3-To judge that degradation rate, this judgment method are with organophosphor agriculture Medicine is completely degraded as judge index.The two has different in the measurement result of degradation rate.Since this paper is related to simultaneously And the degradation to microorganism to organophosphorus pesticide, mechanism of degradation is more complicated, and not simply degrading organic phosphor generation is inorganic PO4 3-Ion, inventor observe that actually part microorganism is during degrading organic phosphor, not will produce inorganic PO4 3-From Son.Therefore, the characteristic manner of the first degradation rate is used in order to which standard is unified herein.
Test result is as follows：
Degradation results of the table 2 for acephatemet (unit of result is %)
Sample number into spectrum 1h degradation rates 2d degradation rates 4d degradation rates
1 39 43 43
2 0 8 23
3 0 7 18
4 0 9 16
5 35 65 91
6 34 59 89
7 34 61 86
8 33 45 61
9 32 47 59
10 36 43 63
Degradation effect of the table 3 for parathion-methyl (unit of result is %)
Sample number into spectrum 1h degradation rates 2d degradation rates 4d degradation rates
1 40 45 45
2 0 7 21
3 0 5 17
4 0 5 16
5 41 68 92
6 38 65 87
7 40 65 85
8 35 48 62
9 37 51 69
10 38 53 72
Degradation effect of the table 4 for Hostathion (unit of result is %)
Sample number into spectrum 1h degradation rates 2d degradation rates 4d degradation rates
1 35 42 42
2 0 13 18
3 0 10 13
4 0 7 15
5 33 62 89
6 32 59 85
7 33 65 88
8 34 45 76
9 33 48 67
10 35 49 70
Test example 2
It is used to test it according to above-mentioned identical method by product 1-15 and comparative example 1-4 to imitate the degradation after pesticide 6d Fruit.As a result display is following (numerical value is degradation rate, unit % in table)：
Sample Acephatemet Parathion-methyl Hostathion
Product 1 97 92 95
Product 2 92 95 90
Product 3 93 90 97
Product 4 95 91 92
Product 5 92 93 95
Product 6 90 89 92
Product 7 91 91 89
Product 8 93 94 88
Product 9 90 93 94
Product 10 94 95 97
Product 11 90 91 91
Product 12 92 91 93
Product 13 93 90 88
Product 14 90 89 92
Product 15 94 90 92
Comparative example 1 39 34 37
Comparative example 2 23 25 21
Comparative example 3 27 26 30
Comparative example 4 41 43 39
Conclusion：
The degradation effect that can be seen that nano-titanium dioxide from above-mentioned degradation experiment is rapider, in 1h substantially Higher degradation rate can be reached.With the extension of time, the catalysis efficiency of one side nano-titanium dioxide itself is also reducing, separately Outside since the ingredient in pesticide mother liquor is relatively complicated, there are more impurity (situation is also similar in actual environment), nanometers two Titanium oxide may be because impurity absorption, deposition or other reasons, can not continue to play degradation function, cannot make pesticide to be measured It is completely degraded.And when microorganism exclusive use, since it needs certain growth proliferation time, and the degradation of itself Journey also will more slowly, so it does not show degradation effect substantially in 1h, degradation effect just gradually shows after 2d.It is logical It crosses and the degradation effect of 2d-6d is observed, it can be seen that nano-titanium dioxide and above-mentioned three kinds of antimicrobial compositions are used, In the case of same amount of application, composition is achieved compared to single dose significantly more preferably degradation effect, it is sufficient to prove them it Between there is complementary relationship so that pesticide to be measured substantial majority within the time of 6d is degraded.In addition, not adding protection In the case of agent, the growth of microorganism is influenced to be significant by nano-titanium dioxide, so as to cause the degradation to organophosphor Effect is also undesirable.The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, It is every according to the technical essence of the invention to any simple modification, equivalent variations made by above example, each fall within the present invention Protection domain within.

Claims (10)

1. a kind of organic pollution complex microorganism degradation agent, it is characterised in that：With the total weight of raw material, including below at Point：Bacillus subtilis (Bacillus subtilis) bacterium powder 1%-20%, nano-titanium dioxide 10-60%, protective agent 10- 20%, other auxiliary materials 20%-60%, wherein bacterium powder contain viable bacteria or spore amount needs to be more than 0.5 hundred million cfu/g, preferably For hundred million cfu/g of 1-5；The preserving number of the bacillus subtilis is CGMCC NO.1.9083, and the protective agent is BHA and plant The combination of object oil.
2. a kind of organic pollution complex microorganism degradation agent according to claim 1, the nano-titanium dioxide grain Diameter is 1-100nm, preferably 10-30nm.
3. a kind of organic pollution complex microorganism degradation agent according to claim 1, the protective agent is according to weight Compare BHA：Vegetable oil is 1:5-20 is combined, wherein the preferred grape seed oil of vegetable oil.
4. a kind of organic pollution complex microorganism degradation agent according to claim 1-3 any one, described other Auxiliary material includes one or more in carrier, wetting agent, dispersant, adhesive, solvent.
5. a kind of preparation method of organic pollution complex microorganism degradation agent according to any one of claims 1-4, Characterized by the following steps：
1) nano-titanium dioxide powder is configured, sol-gal process is used to prepare grain size as the nanometer titanium dioxide within the scope of 1-100nm Titanium；
2) bacterial strain is cultivated, the fermentate of bacterial strain is obtained, bacterium powder is obtained by dry；
3) bacterium powder, vegetable oil and butylated hydroxy anisole (BHA) are weighed according to parts by weight, it is slowly mixed together in blender Even treated bacterium powder；
4) other auxiliary materials are mixed, obtains agent mixture；
5) nano-titanium dioxide that step 1 is prepared is mixed by weight ratio with bacterium powder, adds agent mixture, stirred It mixes in machine and stirs evenly, drying, screening, packaging obtain the organic pollution complex microorganism degradation agent.
6. a kind of preparation method of organic pollution complex microorganism degradation agent according to claim 5, it is characterised in that Wherein step 1) is：First by a certain amount of water and ethyl alcohol by volume 1:4 mixing, and acid or alkali adjusting pH value of solution is added, it obtains To solution as reaction medium, then a certain amount of presoma tetra-n-butyl titanate (TBT) is mixed with ethyl alcohol, before reaction Body is driven, the in the mixed solvent of water and ethyl alcohol is added drop-wise at 75 DEG C, and continues to react at 75 DEG C for 24 hours after being added dropwise, it will Obtained suspension carries out high speed centrifugation, is washed with water and ethyl alcohol, and nano titanium dioxide powder is obtained after dry.
7. a kind of preparation method of organic pollution complex microorganism degradation agent according to claim 5, it is characterised in that Wherein step 2) is：The original strain of bacillus megaterium is aseptically carried out to inclined-plane culture, shaking table culture, hair successively After fermentation tank culture, obtained zymotic fluid is prepared into subtilis spore powder by concentrate drying.
8. a kind of organic pollution complex microorganism degradation agent is in organic dirt of degrading according to any one of claims 1-4 Contaminate the application in object.
9. application according to claim 8, wherein organic pollution refer specifically to pesticide organic matter.
10. application according to claim 9, wherein pesticide organic matter refer specifically in acephatemet, parathion-methyl, Hostathion It is one or more.
CN201810340445.2A 2018-04-16 2018-04-16 A kind of organic pollution complex microorganism degradation agent and preparation method Withdrawn CN108503046A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110040794A (en) * 2019-03-22 2019-07-23 关天明 A kind of improver of water quality of aquatic products and preparation method thereof
CN110468063A (en) * 2019-04-17 2019-11-19 浙江亲水园生物科技有限公司 A kind of microbial solid preparation, preparation method and application
CN110721661A (en) * 2019-10-24 2020-01-24 西南科技大学 Preparation method of efficient adsorption and catalysis dual-function hypha material
CN112760268A (en) * 2021-02-09 2021-05-07 黑龙江大学 Ultraviolet-resistant bacillus and application thereof
CN115400387A (en) * 2022-09-30 2022-11-29 陕西科技大学 Degradable agricultural reflective film composite material and preparation method and use method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110040794A (en) * 2019-03-22 2019-07-23 关天明 A kind of improver of water quality of aquatic products and preparation method thereof
CN110468063A (en) * 2019-04-17 2019-11-19 浙江亲水园生物科技有限公司 A kind of microbial solid preparation, preparation method and application
CN110721661A (en) * 2019-10-24 2020-01-24 西南科技大学 Preparation method of efficient adsorption and catalysis dual-function hypha material
CN110721661B (en) * 2019-10-24 2022-03-25 西南科技大学 Preparation method of efficient adsorption and catalysis dual-function hypha material
CN112760268A (en) * 2021-02-09 2021-05-07 黑龙江大学 Ultraviolet-resistant bacillus and application thereof
CN112760268B (en) * 2021-02-09 2022-11-18 黑龙江大学 Ultraviolet-resistant bacillus and application thereof
CN115400387A (en) * 2022-09-30 2022-11-29 陕西科技大学 Degradable agricultural reflective film composite material and preparation method and use method thereof

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