CN104787977A - Continuous flow integrated electrode bio-membrane reactor and nitrate removal technology - Google Patents

Continuous flow integrated electrode bio-membrane reactor and nitrate removal technology Download PDF

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Publication number
CN104787977A
CN104787977A CN201510185409.XA CN201510185409A CN104787977A CN 104787977 A CN104787977 A CN 104787977A CN 201510185409 A CN201510185409 A CN 201510185409A CN 104787977 A CN104787977 A CN 104787977A
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China
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cathode
chamber
reactor
nitrate
continuous flow
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CN201510185409.XA
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Chinese (zh)
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杨麒
钟宇
李小明
赵建伟
谢丽霞
徐秋翔
姚福兵
高琛林
曾光明
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湖南大学
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Priority to CN201510185409.XA priority Critical patent/CN104787977A/en
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Abstract

The invention provides a continuous flow integrated electrode bio-membrane reactor and a nitrate removal technology. The reactor comprises a cylindrical anode chamber, a cathode chamber and an adsorption chamber. The anode chamber comprises a rodlike anode and a gas vent; the cathode chamber comprises a rotatable sheeted cathode and a gas collection hole; a diaphragm can be added between the anode chamber and the cathode chamber; the anode chamber and the cathode chamber are connected by a flange and fixed by a screw and are convenient to dismount; and the cathode chamber is connected with the adsorption chamber filled with an adsorption material. In the reactor, denitrifying bacteria are inoculated to the sheeted cathode of the cathode chamber; nitrate-containing waste water enters the cathode chamber of the reactor via a constant flow pump and degraded on the surface of the bio-membrane cathode; effluent of the cathode chamber is absorbed and filtered by the adsorption chamber; and sludge and suspended matter in the effluent of the cathode chamber are effectively entrapped. The invention belongs to the application field of a water treatment technique; the whole technology does not require an additional mixing device, an additional organic carbon source or an external source for hydrogen supply, the current efficiency is high, and nitrate nitrogen in a water body can be effectively removed.

Description

The technique of a kind of Continuous Flow integrated electrode biofilm reactor and removal nitrate
Technical field
The invention belongs to the Application Areas of water technology, be specifically related to the technique of a kind of Continuous Flow integrated electrode biofilm reactor and removal nitrate.
Background technology
Along with industrial or agricultural with socioeconomicly to develop rapidly, nitrogenous compound quantity discharged sharply increases, and the accumulation of nitrate in water body is on the rise.The underground water in the most of area of China is in the pollution being all subjected to nitrate in varying degrees, and the water that mankind's long-term drinking NO3-N and NO2-N exceeds standard, can cause sex change hemochrome disease, and the sickness rate of liver cancer, esophagus cancer, cancer of the stomach is increased.At present, regulation nitrate limit value is 10mg/L in GB5749-2006 " drinking water sanitary standard ", but many areas as the nitrate in groundwater concentration of drinking at more than 30mg/L.Therefore the nitrate removed in water body has arrived instant stage.
Present stage, the method for denitration of comparative maturity can be divided into Physical, chemical method and biological process.Wherein, biological denitrification is considered to most potential method of denitration.Needed for denitrifying bacterium, carbon source is different, and biological denitrification is divided into again heterotrophic denitrification and autotrophic denitrification.Different oxygen denitrification has the fast advantage of speed of response, but if the organic carbon source added is inadequate, then water Nitrite Nitrogen just can accumulate in a large number, if the carbon source of adding is excessive, then residual organic carbon source can bring secondary pollution problem; Autotrophic denitrification utilizes inorganic carbon source, and adopt the compound of hydrogen or sulphur as inorganic electron donors, nitrate, as electron acceptor(EA), is converted into harmless nitrogen gas under the effect of autotrophic denitrification bacterium.Along with going deep into of research, some scholars proposes the concept of biofilm-electrode process on autotrophic denitrification basis.Electrode biomembrane denitrification is the process that an electrochemical action and biological denitrification combine, and by domestication biofilm, Microorganism incubation forms denitrification biofilm in cathode surface, and molecular water electrolysis under the effect of impressed current produces hydrogen (H 2), the denitrifying bacteria part on microbial film utilizes the organism in waste water to do electron donor, also has part denitrifying bacteria with H 2for electron donor, be nitrite by nitrate reduction jointly, and be finally reduced to nitrogen (N 2).Electrode biomembrane denitrifying primitive reaction principle is as follows: when wherein adopting carbon anode, carbonic acid gas (as equation 1) can be produced, can be used for the neutral environment maintaining reactor, when adopting metal anode, can be produced oxygen (as equation 2), can be used for nitration reaction.The reaction equation that anode is common:
C+2H 2O→CO 2+4H ++4e -(1)
2H 2O→O 2+4H ++4e -(2)
Cathodic reaction equation:
2H 2O+2e -→H 2+2OH -(3)
1/2O 2+2e -+H 2O→2OH -(4)
2NO 3 -+5H 2→N 2+4H 2O+2OH -(5)
Compared with simple biomembrance process, biological process and electrochemical process mainly organically combine by the advantage of biofilm-electrode process, utilize electrode as biomembranous carrier; Next is the H utilizing micro-electrolytic water to discharge +for denitrifying bacteria provides electron donor, high for electrolytic process redox ability and between microbial film with electrode efficient mass transfer feature is combined, facilitates denitrifying carrying out.
At present, form main still single-cylinder type or the plate type electrode reactor of Electrode-biofilm membrane reactor, anolyte compartment and cathode compartment are not separated, when adopting metal anode, the oxygen produced easily forms aerobic environment near negative electrode microbial film, causes that dissolved oxygen concentration is too high is unfavorable for denitrifying carrying out; Secondly, reactor negative electrode generally adopts fixed electorde, need additional whipping appts to promote contact and the mixing of pollutent and microorganism, and water outlet contains more suspended substance.For above-mentioned defect, need to do further improvement to Electrode-biofilm membrane reactor.
Summary of the invention
Based on the deficiencies in the prior art, one of the technical problem to be solved in the present invention is to provide a kind of Continuous Flow integrated electrode biofilm reactor, comprises columniform anolyte compartment, cathode compartment and adsorption chamber.In the middle of anolyte compartment and cathode compartment, barrier film is housed, effectively can be separated the degraded product of anode and cathode compartment and effectively prevents cathode compartment bacterium from flowing into anolyte compartment.Cathode compartment connects adsorption chamber and carries out adsorption filtration, the mud in the water outlet of effectively catching cathode compartment and suspended substance, makes the concentration of suspension SS in water outlet reach emission standard.
Two of the technical problem to be solved in the present invention is to provide a kind of technique removing nitrate.
For achieving the above object, the present invention takes following technical scheme:
A kind of Continuous Flow integrated electrode biofilm reactor, comprise columniform anolyte compartment (4), cathode compartment (14) and adsorption chamber (17), it is characterized in that: intaking is communicated with the bottom of inlet valve (7) with described cathode compartment (14) through constant flow pump (5); Separated by barrier film between cathode compartment (14) and anolyte compartment (4); Cathode compartment (14) connects the adsorption chamber (17) being filled with sorbing material, and cathode compartment water outlet is discharged through flowing water Valve (15) after adsorption chamber (17) sedimentation and filtration.
Further improvement as technique scheme:
Venting hole and rod anode are contained in described reactor anolyte compartment.
Described reactor cathode compartment contains plate-like cathode, can rotate under the effect of reinforcement agitator.
Described plate-like cathode material is graphite flake, carbon fiber sheet and inert metal sheet.
Described reactor barrier film can adopt fibrous magnesium silicate, proton exchange membrane or composite fibre materials.
The sorbing material that described reactor adsorption chamber is filled is natural zeolite, quartz sand, resin or gac.
Described reactor additional power source adopts voltage stabilized source or potentiostat.
The present invention provides a kind of technique for the treatment of of nitric acid salt simultaneously, it uses above-mentioned Continuous Flow integrated electrode biofilm reactor as process carrier.
Algorithm of the present invention is: (1) will pump in cathode compartment after certain density active sludge (or excess sludge) and sewage mixing, leave standstill 6 ~ 8 hours, mud is made to contact the effect playing microbe inoculation with cathode carrier, all emptying afterwards, enter not containing the sewage of mud more continuously, and strengthen flooding quantity gradually, complete negative electrode biofilm.(2) tame between incubation period, additional certain galvanic current.(3) add the sulphuric acid soln that concentration range is 0.01-0.5mol/L in anolyte compartment, promote H in electrolytic process +migration; Cathode compartment adds pending waste water by constant flow pump, controls strength of current and hydraulic detention time, the continuous operation of realization response device and good treatment effect simultaneously.
Specific works process of the present invention refers to embodiment part.
Tool of the present invention has the following advantages:
(1) by diaphragm application in Electrode-biofilm membranous system, its advantage one is the degraded product that can be separated cathode compartment and anolyte compartment, improve system loading; Two is anodes when adopting metal electrode, and the oxygen that anode electrolysis can be stoped to produce enters cathode compartment, makes cathode compartment formation anoxic and anaerobic environment, promotes denitrifying carrying out, three be prevent cathodic reduction from producing intermediate product as NO 2 -, NO etc. anode again oxidized fall;
(2) negative electrode of cathode compartment is made into rotary vane type, can slow circumvolve, does not need additional whipping device, simplifies operation steps, is easy to running maintenance.
(3) adsorption chamber of reactor can carry out adsorption filtration, can mud in the water outlet of effectively catching cathode compartment and suspended substance.
(4) electrolytic hydrogen production and autotrophic microorganism reduction treatment combine by fixed microorganism, and reaction does not need organic carbon source, and hydrogen is produced by cathodic electrolytic water, and system has operational management convenience, high treating effect.
Describe the present invention in detail below in conjunction with accompanying drawing, it illustrates principle of the present invention as the part of this specification sheets by embodiment, and other side of the present invention, feature and advantage thereof will become very clear by this detailed description.
Accompanying drawing explanation
The accompanying drawing forming a part of the present invention is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.
Fig. 1 is Continuous Flow integrated electrode biofilm reactor structural representation of the present invention;
Fig. 2 is Continuous Flow integrated electrode biofilm reactor anolyte compartment of the present invention side-view;
Fig. 3 is nitrate water inlet, the aqueous concentration schematic diagram of lower concentration in reactor of the present invention;
Fig. 4 is nitrate water inlet, the aqueous concentration schematic diagram of reactor middle and high concentration of the present invention.
Wherein: 1-additional power source; 2-venting hole; 3-rod anode; 4-anolyte compartment; 5-constant flow pump; 6-Flange joint; 7-inlet valve; 8-agitator; 9-isolating joint; 10-graphite brush sheet; 11-gas-collecting pipe; 12-valve; 13-plate-like cathode; 14-cathode compartment; 15-flowing water Valve; 16-sorbing material; 17-adsorption chamber.
Embodiment
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.For sake of convenience, hereinafter as occur " on ", D score, "left", "right" printed words, only represent consistent with the direction, upper and lower, left and right of accompanying drawing itself, restriction effect is not played to structure.
As shown in Figure 1, the Continuous Flow integrated electrode bio-reactor of the present embodiment, comprise anolyte compartment (4), cathode compartment (14) and adsorption chamber (17), waste water containing nitrate passes through the cathode compartment (14) that constant flow pump (5) is with hydrogen autotrophic denitrification bacterium, and water outlet removes suspended substance and large particulate matter by adsorption chamber (17).
As shown in Figure 2, the Continuous Flow integrated electrode bio-reactor anolyte compartment side-view of the present embodiment, dissimilar diaphragm material can be placed in flange connections, is tightly connected by 8 screws and cathode compartment, for convenience detach.
The biofilm domestication of microorganism first will be carried out when the present invention works, to pump in cathode compartment after certain density for 200mL active sludge (or excess sludge) and nitrate wastewater mixing, leave standstill 6 ~ 8 hours, mud is made to contact the effect playing microbe inoculation with cathode carrier, all emptying afterwards, enter continuously more not containing the sewage of mud, and strengthen flooding quantity gradually, complete negative electrode biofilm.Between domestication incubation period, the galvanic current of additional 20mA.Add the sulphuric acid soln that concentration range is 0.01-0.5mol/L in anolyte compartment, promote H in electrolytic process +migration; Cathode compartment adds pending nitrate wastewater by constant flow pump, controls hydraulic detention time simultaneously, and after domestication 15d, water outlet pH is stabilized between 6.5 ~ 8.0, and the clearance of nitrate reaches more than 80%, can judge that domestication completes substantially.
To dispose of sewage example 1:
Structure of reactor is described above, and after above-mentioned biofilm flow process terminates, anolyte compartment adds the sulphuric acid soln that concentration range is 0.1mol/L, and anode adopts 10cm, and diameter is the titanium rod of 0.6cm, and barrier film adopts new type proton exchange membrane, and diameter is 6cm.Cathode compartment passes into the simulation nitrate wastewater of tap water preparation, and negative electrode adopts the carbon fiber sheet of long 8cm, wide 8cm, thick 0.5cm, and strength of current is set as 20mA, and hydraulic detention time is 12 hours.Adsorption chamber is filled with zeolite, utilizes constant flow pump to supply artificial distribution continuously.When nitrate concentration of intaking is 25mg/L (as shown in Figure 3), in water outlet, nitrate concentration is at about 5mg/L, the clearance of nitrate reaches more than 80%, and in water outlet, suspended substance (SS) concentration is less than 1mg SS/L all the time, and does not have the accumulation of nitrite.
To dispose of sewage example 2:
Structure of reactor is described above, and after above-mentioned biofilm flow process terminates, anolyte compartment adds the sulphuric acid soln that concentration range is 0.1mol/L, and anode adopts 10cm, and diameter is the graphite rod of 0.5cm, and barrier film adopts new type proton exchange membrane, and diameter is 6cm.Cathode compartment passes into the simulation nitrate wastewater of tap water preparation, and negative electrode adopts the copper sheet of long 8cm, wide 8cm, thick 0.5cm, and strength of current is set as 20mA, and hydraulic detention time is 12 hours.Adsorption chamber is filled with zeolite, utilizes constant flow pump to supply artificial distribution continuously.When nitrate concentration of intaking is 50mg/L (as shown in Figure 4), in water outlet, nitrate concentration is between 8-12mg/L, lower than the standard gauge threshold value (NO of the existing tap water of China 3 --N≤20mg/L), in water outlet, suspended substance (SS) concentration is less than 1mg SS/L all the time, and does not have the accumulation of nitrite.Compared with example 1, convert different anodes and cathode material, the efficient removal of nitrate can be realized.Visible, Continuous Flow integrated electrode bio-reactor of the present invention and nitrate removal technique can realize effective removal of nitrate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. a Continuous Flow integrated electrode biofilm reactor, comprise columniform anolyte compartment (4), cathode compartment (14) and adsorption chamber (17), it is characterized in that: intaking is communicated with the bottom of inlet valve (7) with described cathode compartment (14) through constant flow pump (5); Separated by barrier film between cathode compartment (14) and anolyte compartment (4); Cathode compartment (14) connects the adsorption chamber (17) being filled with sorbing material, and cathode compartment water outlet is discharged through flowing water Valve (15) after adsorption chamber (17) sedimentation and filtration.
2. Continuous Flow integrated electrode biofilm reactor according to claim 1, is characterized in that: described anolyte compartment (4) are containing venting hole (2) and rod anode (3).
3. Continuous Flow integrated electrode biofilm reactor according to claim 1, is characterized in that: described cathode compartment (14), containing plate-like cathode (13), can rotate under reinforcement agitator (8) effect.
4. plate-like cathode according to claim 3, is characterized in that plate-like cathode material is graphite flake, carbon fiber sheet and inert metal sheet.
5. Continuous Flow integrated electrode biofilm reactor according to claim 1, is characterized in that: described barrier film (6) can adopt fibrous magnesium silicate, proton exchange membrane or composite fibre materials.
6. Continuous Flow integrated electrode biofilm reactor according to claim 1, is characterized in that: the sorbing material that described adsorption chamber (17) is filled is natural zeolite, quartz sand, resin or gac.
7. Continuous Flow integrated electrode biofilm reactor according to claim 1, is characterized in that: described additional power source (1) adopts voltage stabilized source or potentiostat.
8. a technique for Continuous Flow integrated electrode biofilm reactor and removal nitrate, is characterized in that: first the waste water containing nitrate is entered reactor cathode compartment (14) through constant flow pump (5) and inlet valve (7); Nitrate is in the degraded of microbial film cathode surface denitrification, and cathode compartment (14) water outlet carries out adsorption filtration at adsorption chamber (17), the mud in the water outlet of effectively catching cathode compartment and suspended substance; Adsorption chamber (17) is discharged through flowing water Valve (15) and is purified waste water, and completes the removal of nitrate.
CN201510185409.XA 2015-04-17 2015-04-17 Continuous flow integrated electrode bio-membrane reactor and nitrate removal technology CN104787977A (en)

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CN106915803A (en) * 2015-12-24 2017-07-04 湖南大学 A kind of method that electrochemical reactor and anodic-cathodic remove bromate simultaneously
CN106916761A (en) * 2015-12-24 2017-07-04 湖南大学 A kind of bromate degraded composite flora and its Enrichment culture method
CN108455797A (en) * 2018-04-03 2018-08-28 南通华新环保设备工程有限公司 A kind of efficient advanced treating integrating device of sewage minimum discharge

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106915803A (en) * 2015-12-24 2017-07-04 湖南大学 A kind of method that electrochemical reactor and anodic-cathodic remove bromate simultaneously
CN106916761A (en) * 2015-12-24 2017-07-04 湖南大学 A kind of bromate degraded composite flora and its Enrichment culture method
CN108455797A (en) * 2018-04-03 2018-08-28 南通华新环保设备工程有限公司 A kind of efficient advanced treating integrating device of sewage minimum discharge

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Application publication date: 20150722