CN105084530A - Electrochemical assisted biological denitrification technology - Google Patents
Electrochemical assisted biological denitrification technology Download PDFInfo
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- CN105084530A CN105084530A CN201410087584.0A CN201410087584A CN105084530A CN 105084530 A CN105084530 A CN 105084530A CN 201410087584 A CN201410087584 A CN 201410087584A CN 105084530 A CN105084530 A CN 105084530A
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Abstract
The present invention provides an electrochemical assisted biological denitrification method, which is suitable for ammonia nitrogen wastewater with C/N of less than 5 or without an organic carbon source. According to the present invention, under an anaerobic condition, microorganisms are inoculated in ammonia nitrogen wastewater, low voltage (0.3-1.2 V) is applied, and the anode ammoxidation reaction and the cathode denitrification reaction are coupled in the same bio-electrochemical system so as to achieve the full autotrophic biological denitrification from ammonia gas to nitrogen gas; and according to the method, the aeration is not required to carry out the traditional nitration reaction, and the carbon source is not required to be additionally added to complete the denitrification.
Description
One, technical field
The invention belongs to field of environmental biotechnology, be specifically related to a kind ofly assist bio-denitrification technology to the electrochemistry that ammonia nitrogen waste water carries out denitrogenation processing.
Two, background technology
Nitrogen is a kind of principal element causing body eutrophication, and the nitrogen in water body mainly exists with ammonia nitrogen form.If ammonia nitrogen waste water directly discharges without any process, can serious threat ecological safety and HUMAN HEALTH.
Tradition nitrated/the above-mentioned high ammonia-nitrogen wastewater of denitrification biological denitrogenation art breading exist nitrated stage aeration power consumption high, consume basicity, the problems such as the denitrification stage need add organic carbon source in a large number, and processing cost is higher.Although the nitrated-deficiency of denitrification process that novel short distance nitration-anaerobic ammonia oxidation process compensate for tradition to a certain extent, short-cut nitrification technology requires very harsh with anaerobic ammonia oxidation process section to control condition, accurate control is very difficult.Meanwhile, the anaerobic ammonia oxidizing bacteria growth velocity needed for reaction is extremely low, and start anaerobic ammonia oxidation reactor and also acquire a certain degree of difficulty, these deficiencies significantly limit applying of this technique.In addition, the conventional physical chemistry methods such as break point chlorination, ion exchange method, blow-off method, need to add chemical reagent, cause high cost, and these class methods carry out enrichment often through to the transformation between the various form of nitrogen to nitrogen, it is not thoroughly converted into nitrogen, very likely cause secondary pollution, therefore in Technological Economy, still there is many problems, the removal of the ammonia nitrogen bottleneck often becoming the application of these class methods up to standard.In addition, along with the day by day serious of eutrophication problem and people's going deep into nitrogen harm quality of water environment understanding, stain disease emission standard is also increasingly strict to the requirement of nitrogen.Therefore, exploitation high ammonia-nitrogen wastewater Treatment and recovery new technology, reduction energy consumption, material consumption are focus and the difficult point of the research of domestic and international water treatment scientific and engineering circle always.
It is microbiological oxidation electron donor that electrogenesis is breathed, and the electronics of generation is passed to electrode surface via respiratory chain and forms a kind of anaerobic respiration mode of electric current.Nearly ten years, the discovery of electrogenesis microorganism and electrogenesis respiratory mechanism, start and comprised microbiological fuel cell (MicrobialFuelCells, MFCs) with microorganism electrolysis cell (MicrobialElectrolysisCells, MECs) at the research boom of interior bioelectrochemical system (Bio-electrochemicalSystem, BES).BES is as brand-new technology, can realize producing hydrogen (MECs) under organic removal and electrogenesis (MFCs) or low voltage (0.25-0.85V) in sewage simultaneously, therefore a kind of new technology having application prospect is considered to, also for denitrogenation provides a kind of new approaches.
At present, bioelectrochemistry denitrogenation is roughly divided into two classes: 1, by the aerobic cathode compartment in additional independent aerobic biochemical reactive system or double cathode, after traditional nitration reaction, realizes anaerobic denitrifying again at negative electrode; 2, at the biological-cathode of MFC, realize synchronous nitration and denitrification by controlling dissolved oxygen concentration.Above-mentioned reaction all relies on the electronics of anodic oxidation VOCs emission, realizes the reduction of negative electrode nitrate, and sources of nitrate is from additional ammonia oxidation process (abiotic electrochemical reaction).Namely to realize the organic oxidation of anode and negative electrode denitrification and additional auxiliary nitrifying process in a system simultaneously, add the complicacy of system operation undoubtedly, be unfavorable for applying.
Three, summary of the invention
1. know-why:
The present invention is directed to the drawback that existing denitride technology exists, propose a kind of model electrochemical and assist bio-denitrification technology.
Under anaerobic condition, inoculate bed mud in river or sludge sewage, and provide impressed voltage in ammonia nitrogen waste water, through screening and the enrichment of microorganism, anode and negative electrode attached to the microorganism needed for reaction respectively, namely form biological anode and biological-cathode.Through the driving of impressed voltage and the katalysis of microorganism, ammonia release electronics is to anode, and self be oxidized to nitrate and proton, wherein electronics is transferred to negative electrode through external circuit, and nitrate and proton also arrive at negative electrode through solute transfer; Under the katalysis of alive driving and microorganism equally outside, the nitrate of generation receives electronics and the proton of cathode surface, and self is reduced to nitrogen, generates water simultaneously.Concrete reaction is as follows:
Anode: NH
4 ++ 3H
2o → NO
3 -+ 8e
-+ 10H
+
Negative electrode: NO
3 -+ 5e
-+ 6H
+→ 1/2N
2+ 3H
2o4H
++ 3e
-→ 3/2H
2+ H
+
Total reaction: NH
4 +→ 1/2N
2+ 3/2H
2+ H
+Δ Gr0 '=+ 39.4KJ/mol
Through calculation of thermodynamics, impressed voltage needed for above-mentioned reaction is 0.136V, consider to there is electrode reaction overpotential, during experiment, input slot pressure should be greater than this value, and avoid brine electrolysis to occur (under neutrallty condition, the theoretical electromotive force of electrolysis aquatic products hydrogen is 1.23V, and groove pressure during real reaction need reach 2V usually).
This process does not need aeration to carry out traditional nitration reaction completely, completes denitrification without the need to additionally adding carbon source yet, by anode ammonia oxidation process and negative electrode denitrification process being coupling in same reactor, realizes the full autotrophic type biological denitrificaion of ammonia to nitrogen.
2. feature of the present invention:
(1) the ammonia oxidation process of anode and the denitrification process of negative electrode are the auxiliary biological respinse of electrochemistry, and above-mentioned two processes complete in same reactor;
(2) whole reaction process is under anaerobic carried out, without the need to extraneous aeration;
(3) complete denitrification without the need to additionally adding carbon source, whole process is the reaction of full autotrophic.
3. the technique composition needed for technology realization:
Reactor assembly of the present invention comprises: electrochemistry assists biological denitrification reactor, D.C. regulated power supply, reometer, peristaltic pump, nitrogen gathering system, and System's composition is shown in accompanying drawing 1.
4. the operation steps needed for technology realization:
(1) screening of microorganism and enrichment: get appropriate bed mud in river or sludge sewage is inoculated reactor, inject ammonia nitrogen waste water simultaneously, connection circuit afterwards, open D.C. regulated power supply, small-amount voltage is applied to reactor the two poles of the earth, and control temperature, and by internal recycle, certain stirring action is played to reaction, carry out screening and the enrichment of microorganism, use volt ohm-milliammeter record current simultaneously.
Along with the microorganism of screening is in electrode surface enrichment, rising (relative to background current) appears in electric current, and in reactor, ammonia nitrogen concentration starts to reduce, and has nitrogen to produce near negative electrode.When in reactor, ammonia oxidation is complete, declining appears in electric current, and negative electrode stops aerogenesis, and the now screening of microorganism and enrichment complete.
(2) electrochemistry assists biological denitrificaion: after step (1) completes, can adopt and realize denitrogenation in two ways:
A, Continuous Flow: continuously inject ammonia nitrogen waste water to reactor with certain flow rate by peristaltic pump and inlet flume, and water outlet discharged with certain flow rate, keeps other condition constant, starts electrochemistry and assists biological denitrification process.Along with the carrying out of reaction, continue near negative electrode to produce nitrogen, and electric current remains constant substantially.
B, sequence batch (: namely discharge whole mixed solution in reactor, refill ammonia nitrogen waste water, keep other condition constant, start electrochemistry and assist biological denitrification process.When refilling ammonia nitrogen waste water, electric current will rise rapidly, along with the carrying out of reaction, continue to produce nitrogen near negative electrode; Once electric current drops to background value, change whole mixed solution in reactor, carry out next treatment cycle.The rest may be inferred, reaches denitrogenation object.
5. the operational conditions needed for technology realization:
(1), by D.C. regulated power supply for reactor provides electrolysis voltage, voltage is applied between 0.3V ~ 1.2V;
(2) temperature of reaction, is controlled between 15 DEG C ~ 45 DEG C.
Four, accompanying drawing explanation
Fig. 1 is the technology of the present invention System's composition figure, and wherein 1 assist biological denitrification reactor for electrochemistry, 2 is anode, and 3 is negative electrode, and 4 is wire, and 5 is internal recycle, and 6 is hydrogen collection, and 7 is injection port, and 8 is thief hole, and 9 is peristaltic pump.
Five, embodiment
Embodiment 1
Embodiment adopts the technological system shown in accompanying drawing 1, wherein: electrochemistry assists biological denitrification reactor to be 2L (35mm × 100mm × 990mm) square plexiglass box; Negative and positive the two poles of the earth electrode is identical, is plate graphite electrode, electrode size 5mm × 100mm × 300mm, and its Anodic is placed in reactor central authorities, and negative electrode is close to reactor two side and is installed, and cathode and anode spacing is 1cm, and syllogic is arranged in parallel from top to bottom.Ammonia nitrogen waste water is configured by use for laboratory ammonium chloride, containing ammonia about 1000mg/L.After system assembles completes, inject 1800mL ammonia nitrogen waste water, certain bed mud in river 200mL to reactor, form working volume 2000mL.By connection circuit shown in Fig. 1, provide electrolysis voltage 0.8V by D.C. regulated power supply, reactor, by internal recycle accelerated reaction, by heating jacket and temperature controller control temperature 30 DEG C, carries out screening and the enrichment of microorganism.Start after 10 days, electric current starts to rise, and has nitrogen to produce near negative electrode, and in reactor, ammonia nitrogen concentration starts to decline, and within 15 days, after-current reaches peak value 18.61mA, and start afterwards to decline, near negative electrode, aerogenesis stops, and shows that the screening of microorganism and enrichment complete.Afterwards, discharge whole mixed solution in reactor, refill described ammonia nitrogen waste water, other condition remains unchanged, and starts electrochemistry and assists biological denitrification process.Each treatment cycle is about 8 days, and in waste water, the clearance of ammonia nitrogen reaches more than 99%.
Embodiment 2
Embodiment 2 is identical with technological process with the System's composition of embodiment 1, but concrete operating parameter is different, and difference is:
(1) ammonia nitrogen waste water is source-separated urine, takes from certain at village level vacuum source separation system, and without any pre-treatment before using, the content of ammonia is within the scope of 800mg/L ~ 1500mg/L;
(2) reactor does not carry out temperature control, and source-separated urine temperature is within the scope of 15 DEG C ~ 25 DEG C;
In embodiment 2, each treatment cycle maintains 25 days ~ 50 days, and in source-separated urine, the clearance of ammonia nitrogen reaches more than 95%.
Claims (10)
1. the biological denitrification method that an electrochemistry is auxiliary, feature is: the ammonia oxidation process of anode and the denitrification process of negative electrode are the auxiliary biological respinse of electrochemistry, and above-mentioned two processes are carried out in same reactor, be under a kind of anaerobic condition, the biological denitrificaion novel method of full autotrophic.The method achieve nitrifying process and denitrification process completes in same reactor, not needing aeration to carry out traditional nitration reaction, also completing denitrification without the need to additionally adding carbon source.
2. ammonia nitrogen waste water as claimed in claim 1, refers in particular to C/N<5 or not containing the ammonia nitrogen waste water of organic carbon source.
3. the method for claim 1, is characterized in that: required impressed voltage is within the scope of 0.3V ~ 1.2V.
4. the method for claim 1, is characterized in that: the ammonia oxidation process of anode and the denitrification process of negative electrode are the auxiliary biological respinse of electrochemistry, and above-mentioned two PROCESS COUPLING are completed in same system.
5. the method for claim 1, is characterized in that: reaction is under anaerobic carried out, and reactor is without the need to outer oxygen.
6. the method for claim 1, is characterized in that: complete denitrification without the need to additionally adding carbon source, and whole process is the reaction of full autotrophic.
7. the method for claim 1, reaction principle is as follows:
Anode: NH
4 ++ 3H
2o → NO
3 -+ 8e
-+ 10H
+
Negative electrode: NO
3 -+ 5e
-+ 6H
+→ 1/2N
2+ 3H
2o4H
++ 3e
-→ 3/2H
2+ H
+
Total reaction: NH
4 +→ 1/2N
2+ 3/2H
2+ H
+.
8. the method for claim 1, comprises the following steps:
(1) screening of microorganism and enrichment: get appropriate bed mud in river or sludge sewage is inoculated reactor, inject ammonia nitrogen waste water simultaneously, connection circuit afterwards, open D.C. regulated power supply, small-amount voltage is applied to reactor the two poles of the earth, and control temperature, and by internal recycle, certain stirring action is played to reaction, carry out screening and the enrichment of microorganism, use volt ohm-milliammeter record current simultaneously.
Along with the microorganism of screening is in electrode surface enrichment, rising (relative to background current) appears in electric current, and in reactor, ammonia nitrogen concentration starts to reduce, and has nitrogen to produce near negative electrode.When in reactor, ammonia oxidation is complete, declining appears in electric current, and negative electrode stops aerogenesis, and the now screening of microorganism and enrichment complete.
(2) electrochemistry assists biological denitrificaion: after step (1) completes, can adopt and realize denitrogenation in two ways:
A, Continuous Flow: continuously inject ammonia nitrogen waste water to reactor with certain flow rate by peristaltic pump and inlet flume, and water outlet discharged with certain flow rate, keeps other condition constant, starts electrochemistry and assists biological denitrification process.Along with the carrying out of reaction, continue near negative electrode to produce nitrogen, and electric current remains constant substantially.
B, sequence batch (: namely discharge whole mixed solution in reactor, refill ammonia nitrogen waste water, keep other condition constant, start electrochemistry and assist biological denitrification process.When refilling ammonia nitrogen waste water, electric current will rise rapidly, along with the carrying out of reaction, continue to produce nitrogen near negative electrode; Once electric current drops to background value, change whole mixed solution in reactor, carry out next treatment cycle.The rest may be inferred, reaches denitrogenation object.
9. method as claimed in claim 8, is characterized in that: by D.C. regulated power supply for reactor provides electrolysis voltage, applies voltage between 0.3V ~ 1.2V.
10. method as claimed in claim 8, is characterized in that: control temperature of reaction between 15 DEG C ~ 45 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753152A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院生态环境研究中心 | Electrochemistry-aided biological denitrogenation reactor |
| CN105948222A (en) * | 2016-06-23 | 2016-09-21 | 浙江大学 | Anaerobic digestion, denitrification and anaerobic ammonium oxidation bioelectrochemical system and method |
| CN108862577A (en) * | 2017-12-18 | 2018-11-23 | 中山市和智电子科技有限公司 | A kind for the treatment of process of ammonia-nitrogen sewage |
| CN109160603A (en) * | 2018-10-16 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of denitrifying bacterium enrichment method for the exploitation of oil field reinjection water anti-corrosion microbial inoculum |
| WO2020051969A1 (en) * | 2018-09-12 | 2020-03-19 | 浙江大学 | Method and device for treating ammonia-nitrogen wastewater using microbial electrolysis cell assisted sani system |
| CN111573822A (en) * | 2020-05-22 | 2020-08-25 | 盐城工学院 | Bioelectrochemical treatment process for high-ammonia-nitrogen high-sulfate wastewater |
| CN111675310A (en) * | 2020-06-28 | 2020-09-18 | 河海大学 | Horizontal-flow electrochemical denitrification integrated device for urban sewage denitrification |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099953A (en) * | 2008-05-13 | 2011-06-15 | 南加州大学 | Electricity generation using microbial fuel cells |
| CN102351312A (en) * | 2011-09-14 | 2012-02-15 | 中国科学院成都生物研究所 | Bioelectrochemical denitriding reactor and application method thereof |
| CN102765805A (en) * | 2012-08-08 | 2012-11-07 | 大连民族学院 | Filler for sewage treatment, preparation method of filler and sewage treatment method |
-
2014
- 2014-05-16 CN CN201410087584.0A patent/CN105084530A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099953A (en) * | 2008-05-13 | 2011-06-15 | 南加州大学 | Electricity generation using microbial fuel cells |
| CN102351312A (en) * | 2011-09-14 | 2012-02-15 | 中国科学院成都生物研究所 | Bioelectrochemical denitriding reactor and application method thereof |
| CN102765805A (en) * | 2012-08-08 | 2012-11-07 | 大连民族学院 | Filler for sewage treatment, preparation method of filler and sewage treatment method |
Non-Patent Citations (2)
| Title |
|---|
| ZHEN HE 等: ""Electricity Production Coupled to Ammonium in a Microbial Fuel Cell"", 《ENVIRON. SCI. TECHNOL》 * |
| 冉春秋等: ""电极面积对无质子交换膜微生物燃料电池协同去污能力的影响"", 《环境工程学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753152A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院生态环境研究中心 | Electrochemistry-aided biological denitrogenation reactor |
| CN105948222A (en) * | 2016-06-23 | 2016-09-21 | 浙江大学 | Anaerobic digestion, denitrification and anaerobic ammonium oxidation bioelectrochemical system and method |
| CN105948222B (en) * | 2016-06-23 | 2018-09-07 | 浙江大学 | Anaerobic digestion denitrification anaerobic ammoxidation bioelectrochemical system and method |
| CN108862577A (en) * | 2017-12-18 | 2018-11-23 | 中山市和智电子科技有限公司 | A kind for the treatment of process of ammonia-nitrogen sewage |
| WO2020051969A1 (en) * | 2018-09-12 | 2020-03-19 | 浙江大学 | Method and device for treating ammonia-nitrogen wastewater using microbial electrolysis cell assisted sani system |
| US11401185B2 (en) | 2018-09-12 | 2022-08-02 | Zhejiang University | Method and device for treating ammonia-nitrogen wastewater using microbial electrolysis cell assisted SANI system |
| CN109160603A (en) * | 2018-10-16 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of denitrifying bacterium enrichment method for the exploitation of oil field reinjection water anti-corrosion microbial inoculum |
| CN109160603B (en) * | 2018-10-16 | 2021-09-07 | 中国石油化工股份有限公司 | Denitrifying bacterium enrichment method for development of oilfield reinjection water anticorrosive bactericide |
| CN111573822A (en) * | 2020-05-22 | 2020-08-25 | 盐城工学院 | Bioelectrochemical treatment process for high-ammonia-nitrogen high-sulfate wastewater |
| CN111675310A (en) * | 2020-06-28 | 2020-09-18 | 河海大学 | Horizontal-flow electrochemical denitrification integrated device for urban sewage denitrification |
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Application publication date: 20151125 |