CN106045197B - The method for handling pesticide residue and heavy metal Hg in sewage - Google Patents

The method for handling pesticide residue and heavy metal Hg in sewage Download PDF

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Publication number
CN106045197B
CN106045197B CN201610436494.7A CN201610436494A CN106045197B CN 106045197 B CN106045197 B CN 106045197B CN 201610436494 A CN201610436494 A CN 201610436494A CN 106045197 B CN106045197 B CN 106045197B
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sewage
gene
pollution
reductase
pesticide residue
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CN106045197A (en
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朱小明
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Zhongke Zhikang Jiangsu Science And Technology Co ltd
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GUANGZHOU FOODSAFE BIO-TECHNOLOGY Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/0004Oxidoreductases (1.)
    • C12N9/0012Oxidoreductases (1.) acting on nitrogen containing compounds as donors (1.4, 1.5, 1.6, 1.7)
    • C12N9/0036Oxidoreductases (1.) acting on nitrogen containing compounds as donors (1.4, 1.5, 1.6, 1.7) acting on NADH or NADPH (1.6)
    • C12N9/0038Oxidoreductases (1.) acting on nitrogen containing compounds as donors (1.4, 1.5, 1.6, 1.7) acting on NADH or NADPH (1.6) with a heme protein as acceptor (1.6.2)
    • C12N9/0042NADPH-cytochrome P450 reductase (1.6.2.4)
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y106/00Oxidoreductases acting on NADH or NADPH (1.6)
    • C12Y106/02Oxidoreductases acting on NADH or NADPH (1.6) with a heme protein as acceptor (1.6.2)
    • C12Y106/02004NADPH-hemoprotein reductase (1.6.2.4), i.e. NADP-cytochrome P450-reductase
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/306Pesticides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used

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Abstract

It the present invention relates to the use of sewage treatment field, specifically a kind of method for reducing the pollution of mercury and pesticide residue in sewage.This method, which can effectively remove mercury pollution in sewage, has many advantages, such as that high-efficient, nutritional requirement is low, easy to operate and highly-safe, compared with other existing techniques, significantly reduce the cost that sewage mercury and pesticide residual contamination are administered, the efficiency that mercury and pollution by pesticides are administered in sewage is improved, there is very important practical application value.

Description

The method for handling pesticide residue and heavy metal Hg in sewage
The application be the applying date be on June 22nd, 2015, application No. is 201510343959.X, it is entitled " processing The divisional application of the application for a patent for invention of the method for pesticide residue and heavy metal Hg in sewage ".
Technical field
The invention belongs to sewage treatment fields, and in particular to the processing of pesticide residue and heavy metal Hg in sewage belongs to dirt Water comprehensive treatment technique field.
Background technique
In recent decades, chemical pesticide is always the main means kind and pin that Pest organism, the plague of rats are controlled in the agricultural of gardens Amount increases year by year.Chemical pesticide also destroys ecology, polluted environment, often while controlling Pest organism, the plague of rats improves yield The 70% of the pesticide dosage of year more than 500,000 tons will flow into rivers soil, and the pesticide degradation speed having is slow, and pesticide is dense in air Degree will maintain a considerable time, and due to its residual to the pollution in waters, food directly compromise human health and The surface water of the safety of animal, pollution directly pollutes underground water again, and " mankind are just as great tutor Engels introduction Subject the Nature revenge to be administered ".And be ensure grain have a good harvest, pesticide be again it is essential, therefore, detoxification, only Change water resource, comprehensive treatment water environment pollution is very urgent, imperative.
Pollution by pesticides also results in high risks to human health.It is estimated that there are two million people's pesticide poisonings in the whole world every year, 20000 people are dead.Pimentel etc. thinks that the use of pesticide, every year up to 3,000,000,000 dollars, causes society to direct losses caused by the U.S. 8,100,000,000 dollars can be up to the total cost of environment, be equivalent to the 50% of 16,200,000,000 dollars of american chemical pesticide benefit value.So finding The method of pollution by pesticides becomes important subject in processing environment.
In addition, environmental pollution also constantly aggravates with the continuous quickening of China's process of industrialization, administers the mankind and depend on for existence Soil and atmosphere pollution it is extremely urgent.Other than the discharge of strict control pollutant, researchs and develops and be suitble to China's national situation Environmental pollution treatment technology have great importance.Environmental pollution includes heavy metal pollution, pesticide and persistence organic compound Object pollution, chemical fertilizer application pollution etc..With population increase and economic development, a large amount of untreated wastes are shifted to farmland, The soil and water pollution problem that China faces are increasingly severe.The soil pollution in China in recent years is to the area of different scale Domain sexual development, and the generation of various quality of agricultural product is seriously affected.According to incompletely statistics, the soil erosion of China's heavy metal pollution Up to 20,000,000 hectares, the 1/6 of total area under cultivation is accounted for.Because of nearly 7,000,000 hectares of the farmland of Industrial " three Waste " pollution, subtract grain every year Produce 10,000,000,000 kilograms.The half or so of the pollution gross area is accounted in the exceeded area of the elements such as some regional mercury, arsenic, copper, zinc.It is some Main vegetables base Cadmium Pollution in Soils is universal, wherein zinc content in soil is up in some suburbs main facilities vegetable gardening fields 517 mg/kgs, as many as exceeded 5 times.Since soil pollution has concealment, latency and chronicity, serious consequence is only capable of It is caused damages by food to animals and humans health, thus is not easy to be discovered by people.Heavy metal especially in soil has Mobility is small, and the pollution time is long, by being either physically or chemically difficult the features such as thoroughly removing.It improves the ecological environment, protection soil Loamy texture amount, control are polluted with rehabilitating soil, are just able to achieve agricultural safety, this is that face at present one of China is severe and urgent Significant problem.
Currently, there are many pollution by pesticides and the processing method of heavy metal pollution, sum up including chemical treatment, burning, The methods of burial and bioremediation.Chemical treatment method feasibility is strong, but generates a large amount of bronsted lowry acids and bases bronsted lowry during processing, these Substance must also add processing again.Burning may be the degradation most reliable method of these pollutants.But it is released in treatment process big The poison gas of amount, and need a large amount of thermal energy.There are also problems for burial, is mainly manifested in and causes to surrounding soil and water source Secondary pollution.Therefore, it is extremely urgent to develop a kind of processing method that energy conservation and environmental protection is at low cost.
Summary of the invention
One of the objects of the present invention is to provide a kind of methods of pesticide residue and heavy metal Hg in processing sewage.
The present invention is achieved by the following technical scheme:
The method of pesticide residue and heavy metal Hg, includes the following steps: in a kind of processing sewage
(1) it pre-processes: by filtering and precipitating, removing the suspended matter in handled sewage;
(2) main process task: medicament ammonium sulfide, flocculation aid (polyacrylamide) and wadding is added according to mercury concentration in water in foul water fraction Solidifying agent (aluminium polychloride), is added in sewage, and under normal temperature condition, flowing culture 24 hours can remove mercury in sewage;
(3) it post-processes: sewage being again passed by into zeolite and activated carbon adsorption tank, adsorbs pesticide residue;
(4) will treated sewage it is sterile-processed after, direct emission or reuse.
Another technical solution provided by the invention is:
The method of pesticide residue and heavy metal Hg, includes the following steps: in a kind of processing sewage
(1) it pre-processes: by filtering and precipitating, removing the suspended matter in handled sewage;
(2) main process task: the bacterium pseudomonas putida (Pseudomonas putida) of culture to logarithmic growth phase adds Enter into sewage, under normal temperature condition, flowing culture 24 hours can remove mercury in sewage;
(3) it post-processes: sewage being again passed by into zeolite and activated carbon adsorption tank, adsorbs pesticide residue;
(4) will treated sewage it is sterile-processed after, direct emission or reuse.
Preferably, the pseudomonas putida is to be transferred to chtochrome oxidase reductase (P450CYP9G2) He Jingxiu The Pseudomonas putida SPl CGMCC N0.3887 of the gene of the NADPH- cytochrome P450 reductase (POR) of decorations Bacterial strain, the protein sequence of described chtochrome oxidase reductase (P450CYP9G2) coded by said gene is referring to GenBank: The protein sequence of AB096739, the coded by said gene of the modified NADPH- cytochrome P450 reductase (POR) is It carries out being mutated Asp44Ser (table as follows respectively relative to NADPH- cytochrome P450 reductase (POR) original amino acid Show that the 44th Asp sports Ser), Gln74Tyr, Leu96Lys, Asp137Ala, His199Gly, Ile231Gly, Asp296Glu, Asp346Glu, Pro381Cys, Tyr484Lys, Ser519Arg, Gln614His, NADPH- cytochromes The original protein sequences of P450 reductase (POR) coded by said gene are referring to GenBank:L19897.
A series of bacterial strains by genetic modification provided by the invention not only have the effect of preferably going the removal of mercury, go back simultaneously The pesticide residue in sewage can be effectively removed, with good application prospect.
The above method has the advantages that
1, processing method through the invention substantially increases the treatment effect of mercury and pesticide residue, when reducing reaction Between.
2, the conversion bacterial strain of a kind of degrade mercury and pesticide residue, removal efficiency with higher are provided.
In order to make it easy to understand, the present invention will be described in detail by specific embodiment below.It needs to refer in particular to Out, specific example is merely to illustrate, and be not meant to limit the scope of the invention.The ordinary skill people of obvious this field Member can make various modifications and variations to the present invention within the scope of the invention according to illustrating herein, these amendments It is also included in the scope of the present invention with changing.
Specific embodiment
The processing of embodiment 1 mercury and pesticide residue sewage
The concentration of mercury is 30mg/L, Rogor 20mg/L, fenifrothion 20mg/L, Methomyl 20mg/L when wastewater influent.
Pretreatment: by filtering and precipitating, the suspended matter in handled sewage is removed;
Main process task: by bacterium pseudomonas putida disclosed in CN 102373161A of the culture to logarithmic growth phase Pseudomonas putida SPl CGMCC N0.3887, is added in sewage, and under normal temperature condition, flowing culture 24 is small When, mercury in sewage can be removed;
Post-processing: again passing by zeolite and activated carbon adsorption tank for sewage and handle overnight, adsorbs pesticide residue;
Will treated sewage it is sterile-processed after, direct emission or reuse.Through detecting, the concentration of mercury is 2.2mg/L, happy Fruit 15.4mg/L, fenifrothion 14.3mg/L, Methomyl 16.4mg/L.
The transformation and acquisition of 2 degrading pesticide gene of embodiment
According to method disclosed in CN1970741A, clone obtains CYP9G2 and POR gene.It is carried out for POR gene Following transformation, by multiplex PCR by corresponding Asp44Ser (indicating that the 44th Asp sports Ser), Gln74Tyr, Leu96Lys, Asp137Ala, His199Gly, Ile231Gly, Asp296Glu, Gly316Asn, Asp346Glu, Pro381Cys, Tyr484Lys, Ser519Arg, Gln614His, mutational site are introduced between shown in GenBank:L19897 In albumen, to construct different mutant POR genes (preparation method that can refer to the prior art can be obtained).It will mutation POR gene afterwards is connected according to the method for preparing CN1970741A respectively at expression vector together with CYP9G2 gene, will verify Successful recombinant plasmid transformed enters in Pseudomonas putida SPl CGMCC N0.3887 bacterial strain, is detected by PCR, It is constructed successfully.
The verifying of 3 sewage degradation effect of embodiment
The bacterial strain of different mutains will be contained, respectively all in accordance with the method for embodiment 1, verifies the processing to sewage and imitate Fruit.The concentration of mercury is 30mg/L, Rogor 20mg/L, fenifrothion 20mg/L, Methomyl 20mg/L when wastewater influent.To be transferred to not The bacterium of the bacterial strain sum of CYP9G2 and POR gene is mutated as control.Concrete outcome is as follows:
The bacterium that can be seen that POR the and CYP9G2 gene mutation for having imported specific mutation from above result has enhancing The effect for removing the removal of mercury and pesticide, this absolutely prove is not arbitrary change all have preferable effect.Applicant passes through big The verifying of amount just obtains several sites with better effects.

Claims (2)

1. the method for pesticide residue and heavy metal Hg, includes the following steps: in a kind of processing sewage
(1) it pre-processes: by filtering and precipitating, removing the suspended matter in handled sewage;
(2) main process task: the bacterium pseudomonas putida (Pseudomonas putida) of culture to logarithmic growth phase is added to In sewage, under normal temperature condition, flowing culture 24 hours can remove mercury in sewage;
(3) it post-processes: sewage being again passed by into zeolite and activated carbon adsorption tank, adsorbs pesticide residue;
(4) will treated sewage it is sterile-processed after, direct emission or reuse;
The pseudomonas putida is to be transferred to chtochrome oxidase reductase and modified NADPH- Cytochrome P450 The Pseudomonas putida SPl CGMCC N0.3887 bacterial strain of the gene of reductase, the chtochrome oxidase reduction The encoded protein sequence of enzyme gene is referring to GenBank:AB096739, and the modified NADPH- Cytochrome P450 is also The protein sequence of the coded by said gene of protoenzyme is to carry out relative to NADPH- cytochrome P450 reductase original amino acid Following mutation Ile231Gly, the original protein sequences of NADPH- cytochrome P450 reductase coded by said gene referring to GenBank:L19897.
2. a kind of protein variant, it is characterised in that: the variant sequence thereof is as follows relative to the progress of albumen original amino acid It is mutated Ile231Gly, albumen original protein sequences are referring to GenBank:L19897.
CN201610436494.7A 2015-06-22 2015-06-22 The method for handling pesticide residue and heavy metal Hg in sewage Expired - Fee Related CN106045197B (en)

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