CN101624249B - Method for removing nitrate through membrane electrolysis electrochemical hydrogen autotrophic denitrification - Google Patents
Method for removing nitrate through membrane electrolysis electrochemical hydrogen autotrophic denitrification Download PDFInfo
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- CN101624249B CN101624249B CN2008101327335A CN200810132733A CN101624249B CN 101624249 B CN101624249 B CN 101624249B CN 2008101327335 A CN2008101327335 A CN 2008101327335A CN 200810132733 A CN200810132733 A CN 200810132733A CN 101624249 B CN101624249 B CN 101624249B
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Abstract
The present invention relates to a method and a reactor for removing nitrate by combining the processes of membrane electrolysis, electrochemical reduction, hydrogen autotrophic denitrification, membrane separation and the like, which belong to the application field of a water treatment technique. Specifically, a hydrogen ion exchange membrane is used to separate the positive electrode and the negative electrode of an electrolytic bath so as to form a negative electrode chamber and a positive electrode chamber, and a hydrogen autotrophic denitrifying bacteria solution is added in the negative electrode chamber. The positive electrode end and the negative electrode end are applied with direct current, the bacteria in the negative electrode chamber use the hydrogen generated by the negative electrode to perform denitrification so as to remove the nitrate, and simultaneously, the yielding water performs ultrafiltration membrane separation to perform filtration, and the ultrafiltration membrane concentrate flows back into the negative electrode chamber to improve the biomass in the reactor. The positive electrode chamber is added with H2SO4 of which the concentration range is between 0.01 and 0.5 M, H3PO4 or an acid solution thereof prepared according to arbitrary ratio. The method has the advantages of high efficiency for nitrate removal, simple operation and small floor space.
Description
Technical field
The present invention relates to the removal method of nitrate nitrogen in the water, belong to the Application Areas of water technology.The present invention proposes and a kind of the method for removing nitrate in the water is united in effects such as film electrolysis, electrochemical reduction, hydrogen autotrophic denitrification and membrane sepn.Specifically be to utilize the hydrogen ion exchange membrane that anode electrolytic cell and negative electrode are separated formation anolyte compartment and cathode compartment, apply direct current for two sections in cathode and anode, and in cathode compartment, add hydrogen autotrophic denitrification bacterium liquid.The hydrogen that cathode compartment hydrogen autotrophic denitrification bacterium utilizes the electrolysis with ion-exchange film process to produce at negative electrode carries out autotrophic denitrification nitrate reduction is nitrogen.Electrolyzer reaction device effluent adopting ultra-filtration membrane filters, and effectively removes bacterium in the water.The present invention also provides the integrated reactor of realizing said process.
Technical background
Because modern agricultural development, being extensive use of of a large amount of synthetic nitrogenous fertilizer, nitrate becomes one of the most ubiquitous groundwater pollutant.China is a large agricultural country, and in recent years, the pollution problem of China's nitrate in groundwater becomes increasingly conspicuous, and the content of some regional nitrate in groundwater nitrogen is up to 40mg/L (in nitrogen).The harm of nitrate mainly is to bring out siderosis albumen disease in the tap water, and simultaneously, nitrate and nitrite are converted into nitrosamine, have carcinogenic effect.Therefore, the purification of nitrate is a problem demanding prompt solution in the water.
At present, the denitrating technique of comparative maturity can be divided into physical chemistry method of denitration and biological denitrification method.Physico-chemical process mainly comprises ion exchange method, membrane separation process and chemical catalysis.The ion exchange process applicating history is long, and technical maturity all is widely used at many industrial sectors, but has problems such as resin regeneration and discharging of waste liquid.Membrane separation process comprises reverse osmosis and two kinds of methods of electrodialysis, and membrane separating method is simpler than ion-exchange, the producing water ratio height, but film pollution and cost problem have restricted its application.Chemical catalysis is swift in response, easy handling, but exist catalyzer costliness, easy inactivation, and produce by product, cause secondary pollution problems.Biological denitrification is as the method that thoroughly nitrate is converted into nitrogen, obtained at present using the most widely, its principle is that the denitrification by microorganism is reduced to nitrogen with nitrate nitrogen, comprises heterotrophic denitrification and autotrophic denitrification method according to the difference of the required carbon source of microorganism.Heterotrophic denitrification method speed of response is fast, reaction spatiotemporal efficiency height, but mud propagation is comparatively rapid, needs to add organic carbon source simultaneously, causes secondary pollution easily; Autotrophic denitrification utilizes reducing substanceses such as sulphur or hydrogen to be electron donor, nitrate is transformed under as the condition of carbon source at inorganic carbon, and bacterial multiplication is slower, and reaction product is simpler, easily handles.But with sulphur is electron donor, can cause out alkalinity of water to descend, and problems such as water outlet sulfate concentration increase need to replenish Wingdale and regulate basicity, but can cause out the water hardness to increase.Hydrogen is as optimal electron donor, single, the cleaning of reaction product, but problem such as that hydrogen exists is inflammable and explosive, is difficult for transportation, and solubleness is low.Electrochemical hydrogen autotrophic denitrification technology utilizes electrolytic reaction to produce hydrogen, has solved that hydrogen is supplied with and the problem of transportation difficulty, and is easy to operate, and the efficient height becomes the focus of research.
Traditional negative and positive the two poles of the earth non-diaphragm electrochemical hydrogen autotrophic denitrification reactor anode adopts carbon material as sacrificial anode, so the anode oxygen evolution reaction limits this reactor and can only move under lower actuating current (voltage) condition, and reactor load also reduces greatly.The electrolysis with ion-exchange film technology is the new developing technology seventies in 20th century, and its principle utilizes ion-exchange membrane that anode electrolytic cell and negative electrode are separated exactly, is mainly used in chlorine industry at present.Adopt electrolysis with ion-exchange film technology and hydrogen autotrophic denitrification to combine, on the one hand, the existence of the ion-exchange membrane of high conductivity makes that electronic energy accesses transfer between negative electrode and the anode, electric current be able to by; In addition on the one hand, ion-exchange membrane separates the oxygen that anode produces, and makes denitrification process not be subjected to the restriction of anode oxygen evolution reaction, and reactor can apply higher electric current (voltage), and reactor load improves thereupon greatly.Simultaneously, utilize membrane separation technique, make the cathode compartment water outlet by ultrafiltration membrance filter, the microorganism in the effectively catching reactor avoids secondary pollution.The electrolytic electrochemical hydrogen autotrophy of this new membrane membrane bioreactor is with film electrolysis tech, electrochemical hydrogen autotrophic denitrification technology and membrane separation technique three nitrate in an integrated treating water of reactor inner height, simple to operate, the unit volume biomass is many, reaction spatiotemporal efficiency height, non-secondary pollution.
Summary of the invention
The present invention is directed to the nitrate that general physical and chemical process is difficult to remove, propose a kind of based on materialization and collaborative nitrate nitrogen removal method and the relevant reactor of biological process.The present invention has overcome the defective that traditional electrochemical hydrogen autotrophic denitrification technology exists, and by introduce the electrolysis with ion-exchange film process on electrochemical reduction, microorganism denitrification basis, has effectively improved hydrogen utilization ratio and current efficiency.In addition, the present invention introduces the ultra-filtration membrane separating unit in the electrolyzer water outlet, has effectively avoided microbial contamination in the water outlet.
Know-why of the present invention is: utilize the hydrogen ion exchange membrane that electrolyzer yin, yang the two poles of the earth are separated and form cathode compartment and anolyte compartment.The main effect of hydrogen ion exchange membrane is (1) delivered current; (2) allow the hydrogen ion of anolyte compartment to migrate to cathode compartment; (3) prevent that the oxygen that the anolyte compartment produces from entering cathode compartment.Hydrogen ion sees through the hydrogen ion exchange membrane and enters negative electrode and produce hydrogen at cathode surface under electric field action, and the oxygen that anode electrolysis produces separates with cathode compartment under the iris action of hydrogen ion exchange membrane, thereby avoids it to influence the microorganism anti-nitration reaction of cathode compartment.Add the hydrogen autotrophic denitrification bacterium liquid of concentration between the 500mg/L-20000mg/L scope in the cathode compartment, thereby the hydrogen that utilizes negative electrode to produce carries out autotrophic denitrification to nitrate.In addition, for fear of the disadvantageous effect of pH value variation to denitrification process, having added concentration range in the anolyte compartment is the H of 0.01-0.5mol/L
2SO
4, H
3PO
4Or it promotes the migration of hydrogen ion from the anolyte compartment to the cathode compartment according to any acidic solution that gets than preparation.
To the effect that of the present invention: a kind of method based on nitrate in the removal water of membrane electrolysis electrochemical hydrogen autotrophic denitrification effect, it is characterized in that: the water that will contain nitrate is by comprising the electrolyzer of effect of electroreduction nitrate and the denitrification of hydrogen autotrophic denitrification bacterium, the electrolyzer water outlet utilizes ultra filtration unit to filter, the ultra-filtration membrane concentrate recirculation is to cathode compartment, utilize the hydrogen ion exchange membrane with electrolyzer the moon, sun the two poles of the earth separate and form cathode compartment and anolyte compartment, at anode, the negative electrode two ends apply the direct current of range of current at 50mA-3000mA, add the hydrogen autotrophic denitrification bacterium liquid of concentration between the 500mg/L-20000mg/L scope in the cathode compartment, thereby the hydrogen that utilizes negative electrode to produce carries out autotrophic denitrification to nitrate, adds the H that concentration range is 0.01-0.5mol/L in the anolyte compartment
2SO
4, H
3PO
4Or it promotes the migration of hydrogen ion from the anolyte compartment to the cathode compartment, all external recycle pump in yin, yang two Room according to any acidic solution that gets than preparation.
The present invention also provides the reactor of realizing said process.This reactor comprises unit such as electrode (negative electrode, anode), electrolyzer, ultrafiltration.Negative electrode, anode place the electrolyzer two ends respectively, between the hydrogen ion exchange membrane is set to form cathode compartment and anolyte compartment.The cathode compartment of electrolyzer also is the biochemical reaction zone of microbial process simultaneously.Be connected with pipeline between electrolyzer and the ultrafiltration, perhaps be connected with valve with pipeline.In addition, also comprise direct supply in the integrated reactor so that the direct supply of range of current at 50mA-3000mA to be provided, be connected with plain conductor respectively between electrolyzer and negative electrode, the anode.
Foregoing electrolyzer, it is airtight to utilize water seal to carry out, and biological hydrogen autotrophic denitrification bacterium liquid mud directly contacts with negative electrode.It is HCl, the H of 0.01-0.5mol/L that the anolyte compartment adds concentration range
2SO
4, H
3PO
4Or it is according to any acidic solution that gets than preparation, thereby in electrolytic process, promote the H+ migration.In addition, all external recycle pump in cathode and anode two Room is in complete admixture to guarantee two Room solution.The electrolyzer water outlet utilizes ultra filtration unit to filter, to guarantee not contain in the water outlet pollutent such as microorganism; The ultra-filtration membrane concentrate recirculation to cathode compartment improving biomass in the reactor, be connected with valve with pipeline between dense water water outlet and the cathode compartment.
The method and the reactor of the removal nitrate that the present invention proposes have following advantage:
1. water inlet does not need the stripping dissolved oxygen, and the electrochemical cathode reaction can consume the dissolved oxygen in the water into, makes solution keep suitable denitrification anoxic condition.
2. overcome the restriction that traditional electrochemical hydrogen autotrophic denitrification device is subjected to oxygen evolution reaction, negative and positive the two poles of the earth separate, and reactor can apply higher electric current (voltage), thereby can bear than higher reactor load.
3. water outlet can keep the higher biomass of reactor internal ratio through membrane filtration, avoids secondary pollution, and the reactor volume load also improves thereupon.
4. electrochemical appliance is easy and simple to handle, and floor space is little.
5. film effluent adopting separated type is easy to the cleaned and changed of film and maintenance.
Description of drawings:
Electrolyzer detail drawing in Fig. 1 reactor of the present invention;
The total synoptic diagram of Fig. 2 reactor of the present invention;
Reference numeral:
1 negative electrode-Cu sheet; 2 anode DSA electrodes; 3 hydrogen ion exchange membranes; 4 denitrifying activated sludges; 5 recycle pumps; 6 direct supplys; 7 water seals; The water inlet of 8 electrolyzers; 9 electrolyzer water outlets; 10 pressure pumps; 11 membrane separation units; 12 tensimeters; 13 valves; 14 mud reflux; 15 system handles water outlets
Embodiment:
Embodiment 1:
The anolyte compartment applies the H of 0.03mol/L
2SO
4Guarantee that the cathode compartment water outlet is neutral, reactor effective volume 3.0L.To contain NO
3 -The waste water of-N 30mg/L enters this membrane electrolysis electrochemical hydrogen autotrophy membrane bioreactor by water-in, applies electric current 250mA, and the residence time is 5h, sludge concentration 1000-2000mg/L, and in the system handles water outlet, SS does not detect, reactor NO
3 --N clearance＞90%, and do not have NO
2 -Accumulation.
Embodiment 2:
Each operational condition is with embodiment 1, and different is to work as to apply electric current 300mA, and the residence time is 4h, and during sludge concentration 1000-2000mg/L, in the system handles water outlet, SS does not detect, reactor NO
3 --N clearance＞90%, and do not have NO
2 -Accumulation.
Embodiment 3:
Each operational condition is with embodiment 1, and different is to work as to apply electric current 400mA, and the residence time is 3h, and during sludge concentration 1000-2000mg/L, in the system handles water outlet, SS does not detect, reactor NO
3 --N clearance＞90%, and do not have NO
2 -Accumulation.
Embodiment 4:
Each operational condition is with embodiment 1, and different is to work as to apply electric current 550mA, and the residence time is 2h, and during sludge concentration 1000-2000mg/L, in the system handles water outlet, SS does not detect, reactor NO
3 --N clearance＞90%, and do not have NO
2 -Accumulation.
Embodiment 5:
Each operational condition is with embodiment 1, and different is to work as to apply electric current 900mA, and the residence time is 1.25h, and during sludge concentration 2500-3500mg/L, in the system handles water outlet, SS does not detect, reactor NO
3 --N clearance＞90%, and do not have NO
2 -Accumulation.
Claims (2)
1. method based on nitrate in the removal water of membrane electrolysis electrochemical hydrogen autotrophic denitrification effect, it is characterized in that: the water that will contain nitrate is by comprising the electrolyzer of effect of electroreduction nitrate and the denitrification of hydrogen autotrophic denitrification bacterium, the electrolyzer water outlet utilizes ultra filtration unit to filter, the ultra-filtration membrane concentrate recirculation is to cathode compartment, utilize the hydrogen ion exchange membrane with electrolyzer the moon, sun the two poles of the earth separate and form cathode compartment and anolyte compartment, at anode, the negative electrode two ends apply the direct current of range of current at 50mA-3000mA, add the hydrogen autotrophic denitrification bacterium liquid of concentration between the 500mg/L-20000mg/L scope in the cathode compartment, thereby the hydrogen that utilizes negative electrode to produce carries out autotrophic denitrification to nitrate, adds the H that concentration range is 0.01-0.5mol/L in the anolyte compartment
2SO
4, H
3PO
4Or it promotes the migration of hydrogen ion from the anolyte compartment to the cathode compartment, all external recycle pump in yin, yang two Room according to any acidic solution that gets than preparation.
2. the method described in claim 1 is characterized in that: the pole plate that anode adopts graphite cake, carbon fiber sheet, metallic nickel, metal titanium or any one material of titanium-ruthenium to make; The pole plate that negative electrode adopts stainless steel plate, iron plate, aluminium sheet, copper coin, graphite cake, carbon fiber sheet, metallic nickel, metal titanium or any one material of titanium-ruthenium to make.
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| CN2008101327335A CN101624249B (en) | 2008-07-11 | 2008-07-11 | Method for removing nitrate through membrane electrolysis electrochemical hydrogen autotrophic denitrification |
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| CN2008101327335A CN101624249B (en) | 2008-07-11 | 2008-07-11 | Method for removing nitrate through membrane electrolysis electrochemical hydrogen autotrophic denitrification |
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| CN101624249A CN101624249A (en) | 2010-01-13 |
| CN101624249B true CN101624249B (en) | 2011-11-09 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259978A (en) * | 2010-05-31 | 2011-11-30 | 中国地质大学（北京） | Reactor and method for removing nitrate from water |
| CN102249399B (en) * | 2011-06-10 | 2013-07-03 | 北京桑德环境工程有限公司 | Nitrifying reactor suitable for low-temperature environment |
| CN102276026A (en) * | 2011-07-22 | 2011-12-14 | 张小清 | Application method of titanium anode without coating |
| CN102908963A (en) * | 2011-08-01 | 2013-02-06 | 江苏欧赛德钢涂有限公司 | Ceramic membrane filtering apparatus for transferring ethanol by using CO |
| CN104377378B (en) * | 2014-04-28 | 2018-11-09 | 华北电力大学 | A kind of microorganism electrochemical device and method for repairing groundwater azotate pollution |
| CN104355369A (en) * | 2014-11-20 | 2015-02-18 | 哈尔滨工业大学 | Device for removing nitrate nitrogen in water and application method of device |
| CN104874291B (en) * | 2015-06-18 | 2017-03-01 | 中国科学院青岛生物能源与过程研究所 | A kind of detached apparatus and method of electrosynthesis uncoupling membrane |
| CN105693027A (en) * | 2016-03-12 | 2016-06-22 | 常州大学 | Nitrophenol wastewater treatment device |
| CN107055947B (en) * | 2017-03-08 | 2020-06-16 | 中国科学院生态环境研究中心 | Electrolytic enhanced membrane bioreactor and method for treating wastewater by using same |
| CN111807476A (en) * | 2019-04-12 | 2020-10-23 | 江苏省疾病预防控制中心(江苏省公共卫生研究院) | Nitrite reduction device and method in household water purifier |
| CN110129224B (en) * | 2019-05-14 | 2022-03-18 | 中国科学院生态环境研究中心 | Salt-tolerant denitrifying bacterium and preparation method and application of microbial inoculum thereof |
| CN111573834A (en) * | 2020-05-22 | 2020-08-25 | 盐城工学院 | Reactor based on short-cut denitrification electrode is in coordination with anaerobic ammonia oxidation denitrogenation |
| CN111573821A (en) * | 2020-05-22 | 2020-08-25 | 盐城工学院 | Electrode denitrification system based on autotrophic short-cut denitrification-anaerobic ammonia oxidation module |
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