CN1966425A - Conductive water treatment filler - Google Patents

Conductive water treatment filler Download PDF

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CN1966425A
CN1966425A CNA2005100623925A CN200510062392A CN1966425A CN 1966425 A CN1966425 A CN 1966425A CN A2005100623925 A CNA2005100623925 A CN A2005100623925A CN 200510062392 A CN200510062392 A CN 200510062392A CN 1966425 A CN1966425 A CN 1966425A
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filler
water treatment
conductive
parts
treatment filler
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CN100436340C (en
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许炉生
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Zhejiang University of Technology ZJUT
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

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Abstract

There's provided an electric-conductible water-treatment filling on which there's electric-conductible paint. The filling can be elastic filling, combined filling, soft filling, semi-soft filling or chemical engineering filling; the mentioned electric-conductible paint is latex with carbon powder as the main electric-conducting material. The beneficial effects of the invention include the following aspects: (1) short membrane-form time, it only needs 3-14d to form good microbial film; (2) it can degrade the organics quickly: the degrading rate of aromatic hydrocarbon is faster than rate of the optimized obligate degrading bacteria; the nitro and nitroso can be anti-nitrated with no need to add carbon source so that it decreases the density of organics in discharged sewage which is helpful to improve the water quality; (3) it's convenient and easier to get electric-conductible fillings through smearing.

Description

A kind of conductive water treatment filler
(1) technical field
The present invention relates to a kind of novel water treatment filler, this filler obtains conductive capability by coated with conductive coating on the common water treatment filler, be mainly used in the biochemical process water treatment field, as surface water Biological Pretreatment, wastewater biological contact oxidation processing etc., also can be used as the processing that electrode is used for electrochemical reactor and heavy metal wastewater thereby.
(2) background technology
Biological treatment is a main method of removing pollutents such as organism, nitrogen, phosphorus in the water treatment, has obtained widespread use in feedwater, wastewater treatment.Load filler in biochemical reactor, microorganism can increase the residence time of microorganism in reactor in the water treatment filler surface growth, and enhanced system stability improves biological concentration, thereby improves processing efficiency.
At present, the material of water treatment filler mainly is macromolecular materials such as the human relations of hydroformylation dimension, polyethylene, polypropylene, is processed as fiber, elastic yarn and hollow solid, and filling is in water processing reactor.These fillers provide competent apposition growth area for microorganism, but the polymer surface unreactiveness except bond area is provided, can not provide more function.And filling surface is carried out modification, and can not only improve adhering to and growing of microorganism, can also give the filling surface more function.Purpose of the present invention is exactly at filling surface coated conductive layer, forms the Biomembrane electrode filler, and develops novel water technology based on this.
The research of Biomembrane electrode starts from 1988, and U.Fuchs etc. combine bioremediation and electrochemical method, is applied to nitrated-denitrification for Removing Nitrogen.As negative electrode, the metal that designs multiple shape is placed in the cathode container as anode, applies voltage between the electrode with metal vessel for they.NH in the waste water 4 +At first under the nitrococcus effect, be converted into NO 2 -, be converted into N through electrolysis again 2Nineteen ninety, M.Senda is modified at oxydo-reductase on the electrode, is applied in transmitter and the reactor, has realized the electrochemistry control of enzyme reaction.Afterwards, obtaining vigorous growth aspect the enzyme modification chemical electrode.
1992, R.B.Mellor etc. proposed the notion of electrode-bio-reactor first.They are with NO 3 -, after dyestuff matrix phase with electron transport ability such as NO reductase enzyme and safranine T mixes, be coated on cathode surface, make the enzyme electrodes reactor, provide reducing power effectively through immobilized enzyme.1993, people such as Y.Sakibara directly were fixed on denitrifier cathode surface, to the surface water and tap water low concentration of NO 3 -Handle, obtained good effect.When the derivation model, the notion of electrode biomembrane has been proposed, J.R.V.Flora then is referred to as Biomembrane electrode.
At present, international Biomembrane electrode research is the laboratory study of carrying out on the plate electrode of graphite or metal material, does not see industrialization research and development report.In industrial application, the specific surface area that plate electrode can provide generally is no more than 20m 2/ m 3, and large-area plate electrode making, installing, very high technical difficulty is all being arranged in the maintenance, thus cause with high costs, in fact can not be in water treatment large-scale application.
And,, make it have conductive capability to having carried out functional modification in the surface of water treatment filler by the mode of application conductive layer on water treatment filler, can be made into specific surface area up to 250~300m 2/ m 3The three-diemsnional electrode filler.This conductivity type filler is made simple, easy for installation, safeguards, changes simple and easy, has favorable industrial application prospect.
On using, the domestic and international at present reported in literature about Biomembrane electrode concentrates on denitrification, emphasizes that all catholyte produces hydrogen, offers cathode microbial as substrate, with reductive NO 3 -And according to applicant's research, fragrant type organic matter also can obtain good degraded on Biomembrane electrode.To studies show that of chlorobenzene, the degradation speed on Biomembrane electrode can reach 5 times of efficient degrading bacteria degradation speed, and electropotential has been strengthened the degradation capability of microorganism to fragrant type organic matter.Therefore, this novel conductive filler not only can be used for the denitrification water treatment, more can be widely used in the electro-biometric associating catalyzed degradation of water intoxication evil organic matter.
At last, the electric field between the Biomembrane electrode filler electrode has formed electrophoretic action to microorganism, has strengthened the absorption of microorganism on filler, has quickened the growth of microorganism at filling surface.In the processing experiment to wastewater from chemical industry, common fillers needs 20 days microorganism colonization process of growth, can finish in the Biomembrane electrode time last 7 day.
(3) summary of the invention
The present invention promptly is for the conductive water treatment filler that a kind of microorganism colonization time is short, treatment effect is good is provided.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of conductive water treatment filler, described water treatment filler surface-coated has conductive coating paint, described filler is elastic filler or combined stuffing or soft-filler or semi soft packing or chemical filler, and described electrically conducting coating is to be the latex of main electro-conductive material with carbon dust.Described conductive coating paint can directly be bought existing carbon series conductive coating finished product, also can prepare voluntarily by following proportioning: 10~30 parts of carbon dusts, 10~80 parts of polyurethane coating latex or polyacrylate coating, 5~80 parts of auxiliary agents.Described auxiliary agent comprises dispersion agent, stablizer etc., to help the dispersion of carbon dust in coating and stable.
When described urethane or polyacrylate coating were water-borne coatings, described auxiliary agent was a water.Above-mentioned conductive coating paint also can add 1~5 part tensio-active agent, and described tensio-active agent is preferably Sodium dodecylbenzene sulfonate.
Concrete, described conductive coating paint weight is composed as follows: 20 parts of Graphite Powder 99s, 50 parts in water, 50 parts of water soluble acrylic acid ester paints, 5 parts of sodium laurylsulfonates.
Perhaps, described conductive coating paint weight is composed as follows: 10 parts of Graphite Powder 99s, 10 parts of the short silks of carbon fiber, 30 parts in water, 50 parts of aqueous polyurethane coatings, 5 parts of sodium laurylsulfonates.
Or the conductive coating paint weight content is as follows: 10 parts of Shawinigan blacks, 30 parts of polyethylene acetal coating, 60 parts of dimethyl formamides.
Described conductive water treatment filler is mainly used in water treatment, is used for removing organism or the nitro pollutent that anhydrates.During use, the suspension of filler rule is arranged, connect the positive and negative electrode of direct supply respectively, absorption, culturing micro-organisms promptly constitute the Biomembrane electrode water technology.Also filler can be stacked, import direct current, utilize the contact conduction current between the filler with graphite rod, graphite cake, the cathode and anode that forms at random distributes, and culturing micro-organisms absorption growth, handled water flows through from the filler hole, contact filling surface microorganism and obtain handling.
For the suspension type filler, can divide row to hang in the water treating device conductive water treatment filler series connection back apportion, described conductive water treatment filler is with the conductive water treatment filler parallel connection of row's series connection back every row, and adjacent row's conductive water treatment filler is connected with positive source, negative electricity respectively.When hanging two rows, it is linked to each other with power positive cathode respectively get final product, when hanging arrange, then is cross-linked the positive and negative electrode of direct supply more, switches on, and forms electrolytic yin, yang the two poles of the earth (as shown in Figure 1, 2).And for chemical filler, it can be deposited in the reactor, be divided into two chambers with cellular insulant material, in two chamber fillers heap, insert conductor respectively, described conductor is electrically connected with positive source, and another conductor is connected with negative electricity.The effect of cellular insulant material is that the water treatment filler that will connect the different electrical power electrode separates, but water can pass through from its hole.Among the present invention, can adopt insulating film that water treatment filler is divided into two portions, respectively the negative and positive collector electrode be inserted energising, form three-diemsnional electrode (as shown in Figure 3).Active sludge is inoculated into reactor, and add nutritive substance and cultivate.Under electrophoretic action, yin, yang the two poles of the earth will be adsorbed microorganism respectively, and becoming after the growth and maturity can be with the microbial film of electrode (filler) integral coating.This culturing process approximately needs 3~14 days.After the biofilm development maturation, pollutent such as organism, nitro in the water had good removal ability.
Studies show that the arene material of multiple class can be degraded on Biomembrane electrode, and degradation rate is higher than the efficient degrading bacteria of conventional purifying screening.Mass spectrometric detection shows that the arene substrate is all by the open loop of thoroughly degrading, and product is carboxylic-acids such as acetate, valeric acid, and further by the synthetic utilization of microorganism, removes from water.
Under the Biomembrane electrode catalytic condition, all degradeds of open loop faster of various fragrant type organic matters, its approach is enumerated as follows:
Aniline:
Figure A20051006239200081
Oil of mirbane:
Figure A20051006239200082
Chlorobenzene:
Figure A20051006239200083
The beneficial effect of conductive water treatment filler of the present invention is mainly reflected in:
(1) after the gained conductive water treatment filler is connected direct supply, DC electric field causes electrophoretic action, accelerates the apposition growth of microorganism on electrode, and the biofilm time shortens, as long as just can obtain well-grown microbial film in 3~14 days, and common water treatment filler takes 7~30 days.
(2),, accelerated the overall rate of organic matter degradation owing to the existence of electrochemical catalysis effect for the organism in the water.The organic degradation rate of arene surpasses the preferred obligate degradation bacteria of purifying; The microbiotic trade effluent of CODcr 4000mg/L, removed 70% CODcr in 8 hours, and the biodegradability of waste water rises to 0.35 from 0.20, and common biochemical method reaches equal COD clearance then needs residence time more than 48 hours, and the biodegradability of waste water can't improve; For the nitro in the water, nitroso-group, negative electrode directly provides electronics to microorganism, not needing to have realized the denitrification of additional carbon, has reduced the organic concentration in the water, helps increasing water quality.
(3) obtain the conductive biological filler with coating process, use easy to process is simple.The preparation formula of electrically conducting coating is extensive, adds carbon dust and all can obtain electrically conducting coating in various coating, can require to select for use according to different application art.
(4) Figure of description
Fig. 1 is for using the water treating device schematic top plan view of suspension type filler;
Fig. 2 is for using the water treating device diagrammatic cross-section of suspension type filler;
Fig. 3 is for using the water treating device diagrammatic cross-section of stacking formula filler.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1: the conductive water treatment filler preparation
Main raw material: the elastic filler of commercially available φ 15cm (petrochemical industry waters, Shanghai environmental protection factory), water polyacrylic acid coating (Tianjin group converge sealing material factory)
Electrically conducting coating prescription: Graphite Powder 99 2kg, water 5kg, water polyacrylic acid coating 5kg, sodium laurylsulfonate 0.5kg
Above formula material is mixed, dipping elastic filler surface, 80 degree were dried 2 hours down, got product.
Embodiment 2: the conductive water treatment filler preparation
Main raw material: the cascade ring plastic filler that Quanxing, Jiangxi chemical filler company limited produces, the aqueous polyurethane coating that Wenzhou HuanYu Co., Ltd produces
Electrically conducting coating prescription: Graphite Powder 99 1kg, the short silk of carbon fiber 1kg, water 3kg, aqueous polyurethane coating 5kg, sodium laurylsulfonate 0.5kg
Above formula material is mixed, be sprayed on the chemical filler surface, 80 degree were dried 2 hours down, got product.
Embodiment 3: the conductive water treatment filler preparation
Main raw material: the φ 15cm elastic filler that petrochemical industry waters, Shanghai environmental protection factory produces, the polyethylene that Shanghai produces along thing Science and Technology Ltd. of the Johnson ﹠ Johnson first and second aldehyde coating that contract
Electrically conducting coating prescription: Shawinigan black 1kg, the polyethylene first and second aldehyde coating 3kg that contract, dimethyl formamide 6kg
Above formula material is mixed, brush on the elastic filler surface, 80 degree were dried 1 hour down, were warming up to 110 degree thermofixations 2 hours again, got product.
Embodiment 4:
It is regularly arranged in water processing reactor that embodiment 1 gained filler is pressed the plum blossom shape, and be cross-linked the positive and negative electrode (mode of connection is an anchor ear, referring to Fig. 1, Fig. 2) of direct supply, connects the adjustable direct supply of 0~10V, forms electrolytic yin, yang the two poles of the earth.Active sludge is inoculated into reactor, and add nutritive substance and cultivate.Under electrophoretic action, yin, yang the two poles of the earth will be adsorbed the growth microorganism respectively, and becoming after the growth and maturity can be with the microbial film of filler integral coating.This culturing process approximately needs 3~14 days.After the biofilm success, promptly form the Biomembrane electrode water technology.To CODcr is that the treatment effect of the microbiotic trade effluent of 4000mg/L shows: can in 8 hours, remove 70% CODcr, and the biodegradability (BOD of waste water 5/ CODcr) rise to 0.35 from 0.20.
Embodiment 5:
Embodiment 2 gained conductive filler materials are huddled in water processing reactor, are yin, yang collector electrode (referring to Fig. 3) with two carbon-points respectively, and connect direct supply, behind reactor inoculation and the cultivation electrode biomembrane, promptly form the Biomembrane electrode water technology.Processing to simulated wastewater shows: negative electrode provides electronics directly to supply nitro, nitroso-group in the micro-reduction water, in 8 hours, nitro concentration drops to 3mg/L from 40mg/L, not needing to have realized the denitrification of additional carbon, CODcr concentration after handling in the water is low to reach 50mg/L, well below the 100mg/L concentration limit of discharging standards defined.

Claims (12)

1. conductive water treatment filler, it is characterized in that: described water treatment filler surface-coated has conductive coating paint, described filler is elastic filler or combined stuffing or soft-filler or semi soft packing or chemical filler, and described electrically conducting coating is for being the latex of main electro-conductive material with carbon dust.
2. conductive water treatment filler according to claim 1, it is characterized in that: described conductive coating paint main component weight content is as follows:
10~30 parts of carbon dusts
10~80 parts of urethane or polyacrylate coating
5~80 parts of auxiliary agents.
3. conductive water treatment filler as claimed in claim 2 is characterized in that described urethane or polyacrylate coating are water-borne coatings, and described auxiliary agent is a water.
4. conductive water treatment filler as claimed in claim 3 is characterized in that described conductive coating paint also contains 1~5 part tensio-active agent.
5. conductive water treatment filler as claimed in claim 4 is characterized in that described tensio-active agent is a Sodium dodecylbenzene sulfonate.
6. conductive water treatment filler as claimed in claim 5 is characterized in that described conductive coating paint weight is composed as follows:
20 parts of Graphite Powder 99s
50 parts in water
50 parts of water soluble acrylic acid ester paints
5 parts of sodium laurylsulfonates.
7. conductive water treatment filler as claimed in claim 5 is characterized in that described conductive coating paint weight is composed as follows:
10 parts of Graphite Powder 99s
10 parts on carbon fiber
30 parts in water
50 parts of aqueous polyurethane coatings
5 parts of sodium laurylsulfonates.
8. conductive water treatment filler as claimed in claim 1 is characterized in that described conductive coating paint weight content is as follows:
10 parts of Shawinigan blacks
30 parts of polyethylene acetal coating
60 parts of dimethyl formamides.
9. the application of the described conductive water treatment filler of claim 1 in wastewater treatment.
10. the application of conductive water treatment filler as claimed in claim 9 in wastewater treatment is characterized in that described wastewater treatment is for removing organism or nitro pollutent.
11. the application of conductive water treatment filler as claimed in claim 9 in wastewater treatment, it is characterized in that conductive water treatment filler series connection back apportion divides row to hang in the water treating device, described conductive water treatment filler is with the conductive water treatment filler parallel connection of row's series connection back every row, and adjacent row's conductive water treatment filler is connected with positive source, negative electricity respectively.
12. the application of conductive water treatment filler as claimed in claim 9 in wastewater treatment, it is characterized in that conductive water treatment filler is stacked in the water treating device, be divided into two chambers with cellular insulant material, in two chamber fillers heap, insert conductor respectively, described conductor is electrically connected with positive source, and another conductor is connected with negative electricity.
CNB2005100623925A 2005-12-31 2005-12-31 Conductive water treatment filler Expired - Fee Related CN100436340C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219299A (en) * 2011-04-01 2011-10-19 中国科学院成都生物研究所 Wastewater anaerobic oxidation and negative oxygen ion coupled generation device and method
CN109761338A (en) * 2019-03-05 2019-05-17 东北大学 A kind of reinforced electric catalysis biological filler and its application method
CN110117080A (en) * 2019-04-30 2019-08-13 广州博嵩生物环保科技有限公司 A kind of water body purification rope, preparation method and its application
CN112062273A (en) * 2020-08-06 2020-12-11 深圳市广汇源环境水务有限公司 Carbon fiber biological treatment system and method for treating overflow sewage by adopting same
CN116177729A (en) * 2023-01-10 2023-05-30 大连理工大学 Surface conductive coating type biological carrier and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2631957B2 (en) * 1994-07-07 1997-07-16 正和 黒田 Microbial fixed electrode
DE10013457A1 (en) * 2000-03-17 2001-09-20 Andreas Noack Apparatus for purifying water comprises a housing and includes an electrically charged electrodes comprising a porous carbon membrane on a porous support
JP2004137593A (en) * 2002-10-17 2004-05-13 Kenji Shinohara Porous ceramic-water electrode

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219299A (en) * 2011-04-01 2011-10-19 中国科学院成都生物研究所 Wastewater anaerobic oxidation and negative oxygen ion coupled generation device and method
CN102219299B (en) * 2011-04-01 2012-12-19 中国科学院成都生物研究所 Wastewater anaerobic oxidation and negative oxygen ion coupled generation device and method
CN109761338A (en) * 2019-03-05 2019-05-17 东北大学 A kind of reinforced electric catalysis biological filler and its application method
CN109761338B (en) * 2019-03-05 2021-09-07 东北大学 Enhanced electrocatalytic biological filler and use method thereof
CN110117080A (en) * 2019-04-30 2019-08-13 广州博嵩生物环保科技有限公司 A kind of water body purification rope, preparation method and its application
CN110117080B (en) * 2019-04-30 2022-02-08 广州博嵩生物环保科技有限公司 Water body purification rope, preparation method and application thereof
CN112062273A (en) * 2020-08-06 2020-12-11 深圳市广汇源环境水务有限公司 Carbon fiber biological treatment system and method for treating overflow sewage by adopting same
CN112062273B (en) * 2020-08-06 2023-10-13 深圳市广汇源环境水务有限公司 Carbon fiber biological treatment system and method for treating overflow sewage by adopting same
CN116177729A (en) * 2023-01-10 2023-05-30 大连理工大学 Surface conductive coating type biological carrier and preparation method thereof

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