CN106754855A - Embedding type Nanoscale Iron/complex micro organism fungicide and preparation method thereof - Google Patents
Embedding type Nanoscale Iron/complex micro organism fungicide and preparation method thereof Download PDFInfo
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- CN106754855A CN106754855A CN201611044542.4A CN201611044542A CN106754855A CN 106754855 A CN106754855 A CN 106754855A CN 201611044542 A CN201611044542 A CN 201611044542A CN 106754855 A CN106754855 A CN 106754855A
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- nanoscale iron
- triclosan
- micro organism
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 53
- 244000005700 microbiome Species 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 230000000855 fungicidal effect Effects 0.000 title claims abstract description 22
- 239000000417 fungicide Substances 0.000 title claims abstract description 22
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229960003500 triclosan Drugs 0.000 claims abstract description 62
- 241000894006 Bacteria Species 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 241000589614 Pseudomonas stutzeri Species 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 241000588697 Enterobacter cloacae Species 0.000 claims abstract description 22
- 241000589776 Pseudomonas putida Species 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- 229920001817 Agar Polymers 0.000 claims abstract description 15
- 239000008272 agar Substances 0.000 claims abstract description 15
- 241000589158 Agrobacterium Species 0.000 claims abstract description 14
- 241000203749 Gordonia bronchialis Species 0.000 claims abstract description 13
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- 235000015097 nutrients Nutrition 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 241000589159 Agrobacterium sp. Species 0.000 claims description 8
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 claims description 8
- 241001657434 Gordonia sp. Species 0.000 claims description 8
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 8
- 229940119563 enterobacter cloacae Drugs 0.000 claims description 8
- 239000001963 growth medium Substances 0.000 claims description 8
- 235000012054 meals Nutrition 0.000 claims description 8
- 239000002609 medium Substances 0.000 claims description 8
- 239000008363 phosphate buffer Substances 0.000 claims description 7
- 239000001888 Peptone Substances 0.000 claims description 6
- 108010080698 Peptones Proteins 0.000 claims description 6
- 235000015278 beef Nutrition 0.000 claims description 6
- 235000019319 peptone Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000001164 aluminium sulphate Substances 0.000 claims description 5
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 5
- 229910052603 melanterite Inorganic materials 0.000 claims description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000005018 casein Substances 0.000 claims description 3
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical group NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 3
- 235000021240 caseins Nutrition 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000002068 microbial inoculum Substances 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 231100000463 ecotoxicology Toxicity 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 64
- 230000000694 effects Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 102100030497 Cytochrome c Human genes 0.000 description 12
- 108010075031 Cytochromes c Proteins 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 230000002079 cooperative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 230000002438 mitochondrial effect Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 150000004698 iron complex Chemical class 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013076 target substance Substances 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- 108010029541 Laccase Proteins 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 108010059896 Manganese peroxidase Proteins 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 alkenyl halide Chemical class 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000029602 competition with other organism Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
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- 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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
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- 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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to embed type Nanoscale Iron/complex micro organism fungicide and preparation method thereof.The preparation method prepares Nanoscale Iron solution B first by agrobacterium, enterobacter cloacae, rod bacterium, Gordonia bronchialis, pseudomonas putida, Pseudomonas stutzeri, prepares embedding medium agar, PVA, SiO2Solution C, prepares crosslinking agent aluminum sulfate saturation BAS D;Take 15~18% solution Bs respectively by volume, 6~15% thalline A is added in 57~66% solution Cs, is uniformly mixed; in the 1-22% solution Ds for dropping to room temperature in the environment of nitrogen protection, crosslinking Treatment, cleaning; preserve, obtain Nanoscale Iron/complex micro organism fungicide.The present invention improves the degradation efficiency of triclosan using the synergy between Nanoscale Iron and microorganism;Obtained microbial inoculum intensity is high, Ecotoxicology is small, raw material sources are cheap, can be widely used in the water body treatment polluted by triclosan.
Description
Technical field
The present invention relates to triclosan field of waste water treatment, specifically a kind of embedding type Nanoscale Iron for triclosan of degrading/
Complex micro organism fungicide and preparation method thereof.
Background technology
There is triclosan good sterilizing to act on, and possess good security, or even have promotion human body skin new
The moist effect of old metabolism, light.Since being applied to perfumed soap production from 20 century 70s, the range of application of triclosan progressively expands
Greatly, it has been widely used in the production process of personal care articles and medicine, such as detergent, deodorant, cosmetics, sterilizer
Disinfection treatment etc. before tool, and the dispatching from the factory of textile.Triclosan belongs to polar hydrophobic organic matter, be easily deposited on soil,
The solid matters such as bed mud.The lipophilicity of hydrophobic substance makes it easier to accumulate in vivo, also increases triclosan Environmental Residues
Possibility, and the food chain accumulation threat human health for passing through mammal.The easy absorption deposition of this pollutant, persistently
Property, bioconcentration, long-term, uncertain environmental risk is brought to the ecological environment of surrounding.Control to such pollution
With the extensive concern that improvement has caused people.
Biological treatment is current conventional method of wastewater treatment, and the metabolism that this method passes through microorganism will
Polluter in waste water is decomposed, absorbed, so as to reach the purpose of pollution administration.Biological treatment compared with other method, its
Low cost, efficiency high, and easily operate, it is most important that without secondary pollution, therefore, obtain in the treatment of waste water extensively
Application.With expanding economy, the composition of waste water is increasingly complicated, especially when in waste water contain poisonous, difficult degradation organic dirt
During dye thing, due to species, negligible amounts to microorganism of the type organic with special degradation capability in the environment, while it
It is in a disadvantageous position in interspecies competition, therefore, traditional biologic treating technique faces big challenge.
If added in traditional biological treatment system with the microorganism of specific function or some matrix, strengthen it right
The degradation capability of specific pollutants, so as to improve the treatment effect of whole sewage disposal system, our this technologies are called biological
Reinforcement technique.In recent years, nano material is improved reaction rate due to its huge specific surface area and high activity, application
In contaminated soil and groundwater remediation and sewage disposal, and wherein to nano zero valence iron (nano-scale zero-
Valent, nZVI) study relatively many.NZVI is a kind of effective Dehalogenation reduction agent, is just caused early in the eighties in 20th century
The concern of people.Nano zero valence iron can be catalyzed the various organohalogen compounds of reduction, such as:Halogenated alkane, alkenyl halide, halogenated aromatic
Deng hardly degraded organic substance pollutant, nontoxic compound is translated into, can be further while improving its biodegradability
Biodegradation creates favorable conditions.Although nano zero valence iron has many advantages, one is also run into during its application
A little problems, such as the less stable of nano zero valence iron.Nano zero valence iron be easily oxidized and formed iron oxide or
Hydroxide is deposited in nanometer iron surface, so that nano zero valence iron produces passivation.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of degradation efficiency of triclosan is high, and microbial inoculum is strong
Degree height, embedding type Nanoscale Iron/complex micro organism fungicide that Ecotoxicology is small, raw material sources are cheap and its preparation side
Method.
The present invention utilizes chemical means, and Nanoscale Iron and microorganism are carried out into embedding is made composite bacteria agent, can make it three
Cooperative effect is formed in the treatment of chlorine life pollutant, nano iron particles specific surface area and surface-active high can be not only utilized,
The stability and activity of microorganism can also be ensured;The embedding type microbial inoculum being made is adapted to in-situ immobilization and non-secondary pollution.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of embedding type Nanoscale Iron/complex micro organism fungicide, comprises the following steps:
(1) preparation of thalline:
Respectively picking agrobacterium (Agrobacterium sp.), enterobacter cloacae (Enterobactercloacae.),
Rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), pseudomonas putida (Pseudomonas
Putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.) 2 rings are transferred to containing in nutrient solution respectively, and bacterium is in 35-
Cultivated 1-3 days under conditions of 37 DEG C, be seeded in the container containing proliferated culture medium with the volume ratio of 5-18%, at 35-37 DEG C
Under conditions of cultivate 1-3 days, centrifugal treating, the exponential phase cell of the above-mentioned thalline of acquisition;1-2 is washed with phosphate buffer
After secondary;By volume percentage, 5~8% agrobacteriums are taken respectively, 4~6% rod bacteriums, 7~15% enterobacter cloacaes, 10~
19% Gordonia bronchialis, 13~27% pseudomonas putidas and 35~45% Pseudomonas stutzeris mix, and obtain for triclosan drop
The thalline A of solution;
(2) preparation of nanometer ferrous solution:
Using liquid phase reduction, in the liquid-phase system of nitrogen protection, strong reductant KBH4Reduction FeSO4·7H2O is obtained
Fe0, use Fe0The nanometer ferrous solution that concentration is 0.1~0.6g/L is prepared, solution B is designated as;
(3) embedding medium agar, PVA, SiO2The preparation of solution:
Agar, PVA are heated at a temperature of 90-100 DEG C or so and is dissolved completely in clear water, obtained agar quality percentage and contain
It is solution that 5~9%, PVA mass percents are 7.5~15% to measure, and adds SiO2, control SiO2Quality is dense in the mixture
It is 1~3mg/L to spend, to be mixed to be alternately cooled to 50 DEG C, is designated as solution C;
(4) preparation of crosslinking agent aluminum sulfate saturation BAS:
Aluminium Sulphate usp (powder) is dissolved in saturation BAS, the full of the aluminum sulfate that molar concentration is 0.1~1mol/L is obtained
And BAS, it is designated as solution D;
(5) prepared by Nanoscale Iron/complex micro organism fungicide:
Under the conditions of 50-70 DEG C of water bath with thermostatic control, 15~18% solution Bs are taken respectively by volume, 6~15% thalline A adds
Enter in 57~66% solution Cs, be uniformly mixed, in the 1-22% solution Ds for dropping to room temperature in the environment of nitrogen protection,
Crosslinking Treatment, cleaning is preserved, and obtains Nanoscale Iron/complex micro organism fungicide.
Further to realize the object of the invention, it is preferable that the nutrient solution main component is beef extract 6.0g/L,
NaCl5.0g/L, peptone 10.0g/L, soy meal 2.0g/L, pH 6.5, remaining is water.
Preferably, the proliferated culture medium main component is casein 20.0g/L, potassium hydrogen phosphate 3.0g/L, glucose
3.0g/L, soy meal 4.0g/L, sodium chloride 5.0g/L, remaining is water.
Preferably, by volume percentage, the composition of the phosphate buffer is sodium chloride 9.0g/L, potassium chloride
0.3g/L, dipotassium hydrogen phosphate 1.2g/L and potassium dihydrogen phosphate 0.3g/L, remaining is water.
Preferably, the store method of the embedding type Nanoscale Iron/complex micro organism fungicide refers in SPSS
Soak and place in refrigerator and preserved at 4 DEG C.
Preferably, described preservation refers to and soaks in SPSS and place in refrigerator to be preserved at 4 DEG C.
Preferably, the agrobacterium (Agrobacterium sp.), enterobacter cloacae
(Enterobactercloacae.), rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), Pseudomonas putida
Bacterium (Pseudomonas putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.) 2 rings are transferred to containing 30- respectively
In 40mL nutrient solutions.
Preferably, the crosslinking Treatment refers to 10~36h of crosslinking under the conditions of 4-6 DEG C.
Preferably, step 1) described in centrifugal treating refer to the centrifugation 15-30min of 4000-5000rpm.
Preferably, described cleaning is washed with the NaCl solution of 0.8-1.2%.
A kind of embedding type Nanoscale Iron/complex micro organism fungicide for triclosan of degrading, is obtained by above-mentioned preparation method.
The invention has the advantages that:
1) present invention buries type Nanoscale Iron/complex micro organism fungicide, using Nanoscale Iron to the strong reducing property to triclosan, to micro-
Biological adsorptivity, and Nanoscale Iron can be acted on the mitochondrial cytochrome c of microorganism, change the oxidation of cytochrome c
Reduction potential and reinforcement electron transmission ability, therefore composite bacteria agent can produce cooperative effect to collectively promote the degraded of triclosan.
Under the conditions of embodiments of the invention value range, the composite bacteria agent prepared by the present invention is single micro- with same experimental conditions
Bioexperiment and single Nanoscale Iron Experimental comparison, can verify that composite bacteria agent can produce cooperative effect to collectively promote triclosan
Degraded Nanoscale Iron can be acted on the mitochondrial cytochrome c of microorganism, change cytochrome c oxidation-reduction potential and plus
The sub- transmission capacity of forceful electric power.
2) the embedding medium agar raw material sources selected by the present invention are wide, non-toxic inexpensive, with good biocompatibility.
Obtained microbial inoculum intensity is high, Ecotoxicology is low.Solve to be adsorbed in inorganic porous SiO simultaneously2Material microorganism it is unstable
Problem.Nanoscale Iron forms cooperative effect and strengthens triclosan degradation efficiency with microorganism, is adapted to large-scale industrial production.
3) this method is easy to use, is directly delivered in polluted-water after being made microbial inoculum activation, realizes pollution
The in-situ immobilization of water body, is prevented effectively from the loss of microorganism, in the absence of secondary pollution.
Specific embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is further illustrated, but application claims
The scope of protection is not limited to the scope of embodiment statement.
Embodiment step 1) and step 6) in, the nutrient solution main component is beef extract 6.0g/L, NaCl5.0g/L, egg
White peptone 10.0g/L, soy meal 2.0g/L, pH 6.5, remaining is water.
The proliferated culture medium main component be casein 20.0g/L, potassium hydrogen phosphate 3.0g/L, glucose 3.0g/L, greatly
Bean powder 4.0g/L, sodium chloride 5.0g/L, remaining is water.
Embodiment 1
(1) preparation of triclosan degraded bacterium solution
Respectively picking agrobacterium (Agrobacterium sp.), enterobacter cloacae (Enterobactercloacae.),
Rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), pseudomonas putida (Pseudomonas
Putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.) 2 rings, it are transferred in 30mL nutrient solutions respectively, carefully
Bacterium is cultivated 2 days under conditions of 35 DEG C, is seeded in the container of proliferated culture medium with 10% volume ratio, in 35 DEG C of condition
It is lower culture 2 days, with the centrifugation 15min of 5000rpm after, the exponential phase cell of above-mentioned thalline is obtained respectively.Will be above-mentioned
The exponential phase cell of thalline takes out, with phosphate buffer (its main component sodium chloride 9.0g/L, potassium chloride 0.3g/L,
Dipotassium hydrogen phosphate 1.2g/L and potassium dihydrogen phosphate 0.3g/L, remaining is water) wash 2 times.By volume percentage, 5% is taken respectively
Agrobacterium, 5% rod bacterium, 10% enterobacter cloacae, 20% Gordonia bronchialis, 20% pseudomonas putida and 40% Amur are false single
Born of the same parents bacterium mixes, and obtains the thalline for triclosan degraded.Thalline is suspended in physiological saline, standby in 4 DEG C of refrigerations.It is designated as thalline
A;
(2) preparation of nanometer ferrous solution
Using liquid phase reduction, in the liquid-phase system of nitrogen protection, strong reductant KBH4Reduction FeSO4·7H2O is obtained
Fe0, use Fe0It is the nanometer ferrous solution of 0.4g/L to prepare concentration.It is designated as solution B.
(3) embedding medium agar, PVA, SiO2The preparation of solution
Agar, PVA are heated at a temperature of 90 DEG C and are dissolved completely in clear water, it is 5% to obtain agar weight/mass percentage composition,
PVA mass percents are 7.5% solution, add SiO2,SiO2Mass concentration is 1mg/L, alternating to be mixed in the mixture
55 DEG C are cooled to, solution C is designated as;
(4) preparation of crosslinking agent aluminum sulfate saturation BAS
Aluminium Sulphate usp (powder) is dissolved in saturation BAS, the saturation boron of the aluminum sulfate that molar concentration is 0.5mol/L is obtained
Acid solution.It is designated as solution D.
(5) preparation of embedding type microbial inoculum
Under the conditions of 60 DEG C of waters bath with thermostatic control, the solution B of 15%0.1mg/L is taken respectively by volume, 6% thalline A is added
Solution C to 57% (contains the agar of mass percent 5%, 7.5%PVA, 1mg/LSiO2) in, it is uniformly mixed.Protected in nitrogen
Dropped in the environment of shield in 22% solution D (room temperature), 10h is crosslinked under the conditions of 4 DEG C, afterwards with the NaCl solution of 0.9wt%
Cleaning, preservation, obtain Nanoscale Iron/complex micro organism fungicide.
(6) degradation effect of triclosan pollution
Taking Nanoscale Iron complex micro organism fungicide 3mg/L input nutrition liquid-baseds carries out culture 6h, it is direct plungeed into after activating
During 10L concentration is for the triclosan simulating pollution waste water of 5mg/L, Air Exposure 5d, aeration rate is 2L/h.In terms of mass concentration, battalion
Nutrient solution is beef extract 6.0g/L, NaCl5.0g/L, peptone 10.0g/L, soy meal 2.0g/L, pH 6.5, and remaining is water.
Triclosan is determined using Waters high performance liquid chromatography, and condition determination is chromatographic column:Waters C18Post (150 ×
4.6mm I.D., 5 μm);35 DEG C of column temperatures, with acetonitrile/water (75:25, v/v) it is mobile phase, overall flow rate 1.0mL/min, sample size
10 μ L, Detection wavelength is 230nm.Target substance appearance time is approximately 7.2min, and the total detection time of sample is 12min.By surveying
Triclosan initial concentration C in examination water sample0With concentration C after reactiont, obtain triclosan clearance.
2g Nanoscale Iron composite microbial bacterias are added in triclosan 5L waste water using 5mg/L in the present embodiment method treatment water
Agent;6h is cultivated during microbial inoculum directly is put into nutrient solution, is directly delivered after activation and used.Triclosan clearance reaches after Air Exposure 5d
91%, hence it is evident that higher than the control group 28% of single culture (Pseudomonas stutzeri), show embedding type Nanoscale Iron/composite microbial bacteria
Agent has good degradation effect to triclosan, and is substantially better than single culture;Nanoscale Iron is to the strong reducing property of triclosan, to micro-
Biological adsorptivity, and Nanoscale Iron can be acted on the mitochondrial cytochrome c of microorganism, change the oxidation of cytochrome c
Reduction potential and reinforcement electron transmission ability;Composite bacteria agent can produce cooperative effect to collectively promote the degraded of triclosan.Nanometer
Strong reducing property of the iron to triclosan, the adsorptivity to microorganism, and Nanoscale Iron can be with the mitochondrial cytochrome cs of microorganism
Effect, changes the oxidation-reduction potential of cytochrome c and strengthens electron transmission ability, and composite bacteria agent can produce cooperative effect to be total to
With the degraded for promoting triclosan.
Embodiment 2
(1) preparation of triclosan degraded bacterium solution
Respectively picking agrobacterium (Agrobacterium sp.), enterobacter cloacae (Enterobactercloacae.),
Rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), pseudomonas putida (Pseudomonas
Putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.) 2 rings, it are transferred in 30mL nutrient solutions respectively, carefully
Bacterium is cultivated 2 days under conditions of 35 DEG C, is seeded in the container of proliferated culture medium with 10% volume ratio, in 35 DEG C of condition
It is lower culture 2 days, with the centrifugation 15min of 5000rpm after, the exponential phase cell of above-mentioned thalline is obtained respectively.
The exponential phase cell of above-mentioned thalline is taken out, with phosphate buffer (its main component sodium chloride 9.0g/L,
Potassium chloride 0.3g/L, dipotassium hydrogen phosphate 1.2g/L and potassium dihydrogen phosphate 0.3g/L, remaining is water) wash 2 times.By percent by volume
Meter, takes 5% agrobacterium respectively, 5% rod bacterium, 10% enterobacter cloacae, 20% Gordonia bronchialis, 20% pseudomonas putida and
40% Pseudomonas stutzeri mixes, and obtains the thalline for triclosan degraded.Thalline is suspended in physiological saline, in 4 DEG C of refrigerations
It is standby.It is designated as thalline A;
(2) preparation of nanometer ferrous solution
Using liquid phase reduction, in the liquid-phase system of nitrogen protection, strong reductant KBH4Reduction FeSO4·7H2O is obtained
Fe0, use Fe0It is the nanometer ferrous solution of 0.4g/L to prepare concentration.It is designated as solution B.
(3) embedding medium agar, PVA, SiO2The preparation of solution
Agar, PVA are heated at a temperature of 90 DEG C and are dissolved completely in clear water, it is 7% to obtain agar weight/mass percentage composition,
PVA mass percents are 11.5% solution, add SiO2,SiO2Mass concentration is 2mg/L, friendship to be mixed in the mixture
For being cooled to 55 DEG C, solution C is designated as;
(4) preparation of crosslinking agent aluminum sulfate saturation BAS
Aluminium Sulphate usp (powder) is dissolved in saturation BAS, the saturation boron of the aluminum sulfate that molar concentration is 0.5mol/L is obtained
Acid solution.It is designated as solution D.
(5) preparation of embedding type microbial inoculum
Under the conditions of 60 DEG C of waters bath with thermostatic control, the solution B of 16%0.4mg/L is taken respectively by volume, 10% thalline A is added
Solution C to 61% (contains the agar of mass percent 7%, 11.5%PVA, 2mg/L SiO2) in, it is uniformly mixed.In nitrogen
Dropped in the environment of protection in 13% solution D (room temperature), 23h is crosslinked under the conditions of 4 DEG C, the NaCl with 0.9wt% is molten afterwards
Liquid cleaning, preservation, obtain Nanoscale Iron/complex micro organism fungicide.
(6) degradation effect of triclosan pollution
Taking Nanoscale Iron complex micro organism fungicide 3mg/L input nutrition liquid-baseds carries out culture 6h, it is direct plungeed into after activating
During 10L concentration is for the triclosan simulating pollution waste water of 5mg/L, Air Exposure 5d, aeration rate is 2L/h.In terms of mass concentration, battalion
The composition of nutrient solution is beef extract 6.0g/L, NaCl5.0g/L, peptone 10.0g/L, soy meal 2.0g/L, pH 6.5, and remaining is
Water.
Using the present embodiment method, 2g Nanoscale Iron complex microorganism compound bacterias are added in the 5L waste water of triclosan containing 5mg/L
Agent;After activation, 6h is cultivated during microbial inoculum directly is put into nutrient solution, directly deliver and use.Triclosan clearance after Air Exposure 5d
Up to 98%, hence it is evident that higher than the control group 32% of single culture (Pseudomonas stutzeri), show embedding type Nanoscale Iron/complex microorganism
Microbial inoculum has good degradation effect to triclosan, and is substantially better than single culture.Because strong reduction of the Nanoscale Iron to triclosan
Property, to the adsorptivity of microorganism, and Nanoscale Iron can be acted on the mitochondrial cytochrome c of microorganism, change cytochrome c
Oxidation-reduction potential and strengthen electron transmission ability.Therefore composite bacteria agent can produce cooperative effect to collectively promote triclosan
Degraded.
Triclosan is determined using Waters high performance liquid chromatography, and condition determination is chromatographic column:Waters C18Post (150 ×
4.6mm I.D., 5 μm);35 DEG C of column temperatures, with acetonitrile/water (75:25, v/v) it is mobile phase, overall flow rate 1.0mL/min, sample size
10 μ L, Detection wavelength is 230nm.Target substance appearance time is approximately 7.2min, and the total detection time of sample is 12min.
Embodiment 3
(1) preparation of triclosan degraded bacterium solution
Respectively picking agrobacterium (Agrobacterium sp.), enterobacter cloacae (Enterobactercloacae.),
Rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), pseudomonas putida (Pseudomonas
Putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.) 2 rings, it are transferred in 30mL nutrient solutions respectively, carefully
Bacterium is cultivated 2 days under conditions of 35 DEG C, is seeded in the container of proliferated culture medium with 10% volume ratio, in 35 DEG C of condition
It is lower culture 2 days, with the centrifugation 15min of 5000rpm after, the exponential phase cell of above-mentioned thalline is obtained respectively.
The exponential phase cell of above-mentioned thalline is taken out, with phosphate buffer (its main component sodium chloride 9.0g/L,
Potassium chloride 0.3g/L, dipotassium hydrogen phosphate 1.2g/L and potassium dihydrogen phosphate 0.3g/L, remaining is water) wash 2 times.By percent by volume
Meter, takes 5% agrobacterium respectively, 5% rod bacterium, 10% enterobacter cloacae, 20% Gordonia bronchialis, 20% pseudomonas putida and
40% Pseudomonas stutzeri mixes, and obtains the thalline for triclosan degraded.Thalline is suspended in physiological saline, in 4 DEG C of refrigerations
It is standby.It is designated as thalline A;
(2) preparation of nanometer ferrous solution
Using liquid phase reduction, in the liquid-phase system of nitrogen protection, strong reductant KBH4Reduction FeSO4·7H2O is obtained
Fe0, use Fe0It is the nanometer ferrous solution of 0.4g/L to prepare concentration.It is designated as solution B.
(3) embedding medium agar, PVA, SiO2The preparation of solution
Agar, PVA are heated at a temperature of 90 DEG C and are dissolved completely in clear water, it is 9% to obtain agar weight/mass percentage composition,
PVA mass percents are 15% solution, add SiO2,SiO2Mass concentration is 3mg/L, alternating to be mixed in the mixture
55 DEG C are cooled to, solution C is designated as;
(4) preparation of crosslinking agent aluminum sulfate saturation BAS
Aluminium Sulphate usp (powder) is dissolved in saturation BAS, the saturation boron of the aluminum sulfate that molar concentration is 0.5mol/L is obtained
Acid solution.It is designated as solution D.
(5) preparation of embedding type microbial inoculum
Under the conditions of 60 DEG C of waters bath with thermostatic control, the solution B of 18%0.6mg/L is taken respectively by volume, 15% thalline A is added
Solution C to 66% (contains the agar of mass percent 9%, 15%PVA, 3mg/L SiO2) in, it is uniformly mixed.Protected in nitrogen
Dropped in the environment of shield in 1% solution D (room temperature), 36h is crosslinked under the conditions of 4 DEG C, the NaCl solution with 0.9wt% is clear afterwards
Wash, preserve, obtain Nanoscale Iron/complex micro organism fungicide.
(6) degradation effect of triclosan pollution
Taking Nanoscale Iron complex micro organism fungicide 3mg/L input nutrition liquid-baseds carries out culture 6h, it is direct plungeed into after activating
During 10L concentration is for the triclosan simulating pollution waste water of 5mg/L, Air Exposure 5d, aeration rate is 2L/h.In terms of mass concentration, battalion
The composition of nutrient solution is beef extract 6.0g/L, NaCl5.0g/L, peptone 10.0g/L, soy meal 2.0g/L, pH 6.5, and remaining is
Water.
Using the present embodiment method, 2g Nanoscale Iron complex microorganism compound bacterias are added in the 5L waste water of triclosan containing 5mg/L
Agent;After activation, 6h is cultivated during microbial inoculum directly is put into nutrient solution, directly deliver and use.Triclosan clearance after Air Exposure 5d
Up to 96%, hence it is evident that higher than the control group 25% of single culture (Pseudomonas stutzeri), show embedding type Nanoscale Iron/complex microorganism
Microbial inoculum has good degradation effect to triclosan, and is substantially better than single culture.Because strong reduction of the Nanoscale Iron to triclosan
Property, to the adsorptivity of microorganism, and Nanoscale Iron can be acted on the mitochondrial cytochrome c of microorganism, change cytochrome c
Oxidation-reduction potential and strengthen electron transmission ability.Therefore composite bacteria agent can produce cooperative effect to collectively promote triclosan
Degraded.
Triclosan is determined using Waters high performance liquid chromatography, and condition determination is chromatographic column:Waters C18Post (150 ×
4.6mm I.D., 5 μm);35 DEG C of column temperatures, with acetonitrile/water (75:25, v/v) it is mobile phase, overall flow rate 1.0mL/min, sample size
10 μ L, Detection wavelength is 230nm.Target substance appearance time is approximately 7.2min, and the total detection time of sample is 12min.
In the present invention, the synergy of Nanoscale Iron and microorganism, prepared by the experiment proof present invention meets microbial inoculum in phase
Under same experiment condition, effect is better than single microorganism agrobacterium (Agrobacterium sp.), enterobacter cloacae respectively
(Enterobactercloacae.), rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), Pseudomonas putida
Bacterium (Pseudomonas putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.).Nanoscale Iron is to triclosan
Strong reducing property, the adsorptivity to microorganism, and Nanoscale Iron can be acted on the mitochondrial cytochrome c of microorganism, change thin
The oxidation-reduction potential and reinforcement electron transmission ability of born of the same parents' pigment c, therefore composite bacteria agent can produce cooperative effect to collectively promote
The degraded of triclosan.The problem easily suppressed by mesostate during strain degradation triclosan is overcome, while will
Nanoscale Iron and microorganism carry out embedding and are made microbial inoculum, can not only utilize nano iron particles specific surface area and surface-active high,
The stability and activity of microorganism can also be ensured, make it that cooperative effect, clearance are formed in the treatment of triclosan pollutant
Substantially increase.The embedding type microbial inoculum being made is adapted to rest in situ and non-secondary pollution.
According to the report of Related Bacteria degraded triclosan:Fungal laccase (laccases)/redox mediators system degraded
The degradation rate of triclosan is 90% [Murugesan K, Chang Y Y, Kim Y M, et al.Enhanced
transformation of triclosanbylaccase in the presence of redox mediators[J]
.Water Research,2010,44(1):298-308.], white-rot fungi is also 90% [Inoue to the degradation rate of triclosan
Y,Hata T,Kawai S,et al.Elimination and detoxification of triclosan by
manganeseperoxidase from white rot fungus[J].Journal of Hazardous Materials,
2010,180(1‐3):764‐767.].These bacteriums are less than microbial inoculum of the invention, therefore the microbial inoculum to the degradation efficiency of triclosan
Had a good application prospect in terms of triclosan waste water is processed.Embedding type Nanoscale Iron single microorganism microbial inoculum prepared by the present invention
It is not only advantageous in the degraded to triclosan.And the embedding medium can utilize nano iron particles specific surface area high and surface
Activity, it can also be ensured that the stability and activity of microorganism.The embedding type microbial inoculum being made is adapted to in-situ immobilization and non-secondary pollution.
The embedding medium being made only need simply activation after by come into operation, the prospect with large-scale industrial production.
Embodiments of the present invention are simultaneously not restricted to the described embodiments, other any real without departing from spirit of the invention
Matter and the change, modification, replacement made under principle, combine, simplify, should be equivalent substitute mode, being included in the present invention
Protection domain within.
Claims (10)
1. the preparation method of embedding type Nanoscale Iron/complex micro organism fungicide, it is characterised in that comprise the following steps:
(1) preparation of thalline:
Picking agrobacterium (Agrobacterium sp.), enterobacter cloacae (Enterobactercloacae.), shaft-like respectively
Bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), pseudomonas putida (Pseudomonas putida.), apply
Family name pseudomonad (Pseudomonas stutzeri.) 2 rings are transferred to containing in nutrient solution respectively, condition of the bacterium at 35-37 DEG C
Lower culture 1-3 days, is seeded in the container containing proliferated culture medium with the volume ratio of 5-18%, is trained under conditions of 35-37 DEG C
Support 1-3 days, centrifugal treating, obtain the exponential phase cell of above-mentioned thalline;After 1-2 times being washed with phosphate buffer;Press body
Product percentages, take 5~8% agrobacteriums, 4~6% rod bacteriums, 7~15% enterobacter cloacaes, 10~19% Ge Dengshi respectively
Bacterium, 13~27% pseudomonas putidas and 35~45% Pseudomonas stutzeris mix, and obtain the thalline A for triclosan degraded;
(2) preparation of nanometer ferrous solution:
Using liquid phase reduction, in the liquid-phase system of nitrogen protection, strong reductant KBH4Reduction FeSO4·7H2O obtains Fe °,
The nanometer ferrous solution that concentration is 0.1~0.6g/L is prepared with Fe °, solution B is designated as;
(3) embedding medium agar, PVA, SiO2The preparation of solution:
Agar, PVA are heated at a temperature of 90-100 DEG C or so and is dissolved completely in clear water, obtaining agar weight/mass percentage composition is
5~9%, PVA mass percent are 7.5~15% solution, add SiO2, control SiO2Mass concentration is 1 in the mixture
~3mg/L, it is to be mixed to be alternately cooled to 50 DEG C, it is designated as solution C;
(4) preparation of crosslinking agent aluminum sulfate saturation BAS:
Aluminium Sulphate usp (powder) is dissolved in saturation BAS, the saturation boron of the aluminum sulfate that molar concentration is 0.1~1mol/L is obtained
Acid solution, is designated as solution D;
(5) prepared by Nanoscale Iron/complex micro organism fungicide:
Under the conditions of 50-70 DEG C of water bath with thermostatic control, 15~18% solution Bs are taken respectively by volume, 6~15% thalline A is added to
In 57~66% solution Cs, it is uniformly mixed, in the 1-22% solution Ds for dropping to room temperature in the environment of nitrogen protection, crosslinking
Treatment, cleaning is preserved, and obtains Nanoscale Iron/complex micro organism fungicide.
2. preparation method according to claim 1, it is characterised in that the nutrient solution main component is beef extract 6.0g/
L, NaCl5.0g/L, peptone 10.0g/L, soy meal 2.0g/L, pH 6.5, remaining is water.
3. preparation method according to claim 1, it is characterised in that the proliferated culture medium main component is casein
20.0g/L, potassium hydrogen phosphate 3.0g/L, glucose 3.0g/L, soy meal 4.0g/L, sodium chloride 5.0g/L, remaining is water.
4. according to its preparation method described in claim 1, it is characterised in that by volume percentage, the phosphate buffer
Composition be sodium chloride 9.0g/L, potassium chloride 0.3g/L, dipotassium hydrogen phosphate 1.2g/L and potassium dihydrogen phosphate 0.3g/L, remaining is
Water.
5. according to the preparation method described in claim 1, it is characterised in that described preservation refers to be soaked in SPSS
And place in refrigerator and preserved at 4 DEG C.
6. according to the preparation method described in claim 1, it is characterised in that the agrobacterium (Agrobacterium sp.), the moon
Enterobacter cloacae (Enterobactercloacae.), rod bacterium (Bacillus sp.), Gordonia bronchialis (Gordonia sp.), evil
Smelly pseudomonad (Pseudomonas putida.), Pseudomonas stutzeri (Pseudomonas stutzeri.) 2 rings turn respectively
In moving on to nutrient solution containing 30-40mL.
7. according to the preparation method described in claim 1, it is characterised in that the crosslinking Treatment refers to be crosslinked 10 under the conditions of 4-6 DEG C
~36h.
8. according to the preparation method described in claim 1, it is characterised in that step 1) described in centrifugal treating refer to 4000-
The centrifugation 15-30min of 5000rpm.
9. according to the preparation method described in claim 1, it is characterised in that described cleaning is with the NaCl solution of 0.8-1.2%
Washing.
10. a kind of embedding type Nanoscale Iron/complex micro organism fungicide for triclosan of degrading, it is characterised in that it is by claim
Preparation method described in any one of 1-9 is obtained.
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