CN104787937A - Method for performing electrolytic treatment on high-concentration ammonia nitrogen wastewater by using three-dimensional electrodes - Google Patents
Method for performing electrolytic treatment on high-concentration ammonia nitrogen wastewater by using three-dimensional electrodes Download PDFInfo
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Abstract
The invention discloses a method for performing electrolytic treatment on high-concentration ammonia nitrogen wastewater by using three-dimensional electrodes. The method comprises the following steps: (1) treating the high-concentration ammonia nitrogen wastewater by using a three-dimensional electrode electrolysis device; (2) enabling effluent water treated by the three-dimensional electrode electrolysis device to enter a flocculation reaction tank, adding chemicals for flocculation reaction treatment, and adding sodium hydroxide to regulate the pH of the wastewater to 8-9, wherein the reaction treatment time is 10-30 minutes; (3) enabling effluent water after the flocculation reaction treatment to enter a vertical flow reaction sedimentation tank for sedimentation treatment, wherein the sedimentation reaction time is 60-180 minutes; (4) enabling effluent water after the sedimentation treatment to enter a clean water tank. According to the method, by virtue of characteristics of high electrolytic current efficiency, big specific surface area, strong oxidative degradation ability and the like of the three-dimensional electrodes, the purpose of simply, efficiently and rapidly degrading the high-concentration ammonia nitrogen is achieved, and the wastewater reaches the discharge standard.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of method utilizing three-dimensional electrode electrolysis process high-concentration ammonia nitrogenous wastewater.
Background technology
Ammonia nitrogen is the nutrient substance in water body, can body eutrophication be caused, make the waterplant such as pasture and water and blue-green algae amount reproduction, the dissolved oxygen in luxus consumption water, force the hydrobionts such as fish dead because of anoxic, and ammonia nitrogen waste water is to fish and the also toxic effect of some hydrobiont.In addition, when the reusing sewage containing a small amount of ammonia nitrogen is in industry, to some metal, particularly copper has corrosive nature, can also promote the breeding of microorganism in water pipe and watering equipment, forms biofouling, blocking pipe and equipment.Ammonia nitrogen waste water wide material sources, quantity discharged are big, and it administers the important factor having become restriction industry development.
The method of current process high-concentration ammonia nitrogenous wastewater has: chemical precipitation method, blow-off method, break point chlorination method, catalytic oxidation, biological process etc.Chemical precipitation method removal effect well can form compound manure magnesium ammonium phosphate simultaneously, but processing cost is higher, easily causes remaining phosphorus secondary pollution; Blow-off method is materialization denitride technology conventional at present, but there is the frequent fouling of stripping tower, and during low temperature, ammonia nitrogen removal efficiency is low, the secondary pollution problems of stripping gas; Break point chlorination method nitric efficiency is high, but by product chloramines and chlorinatedorganic easily cause secondary pollution; Catalytic oxidation purification efficiency is high, but catalyzer easily runs off, and equipment easily corrodes; Traditional biological method is suitable only for process Low Concentration Ammonia Containing Wastewater, must carry out pre-treatment before process high-concentration ammonia nitrogenous wastewater.
Summary of the invention:
Technical problem to be solved by this invention is the deficiency overcoming existing process high-concentration ammonia nitrogenous wastewater technology, reach object that is easy, efficient, fast degradation ammonia nitrogen in high density, a kind of method utilizing three-dimensional electrode electrolysis process high-concentration ammonia nitrogenous wastewater is provided, reaches national grade one discharge standard to realize water outlet.
For solving the problems of the technologies described above, the present invention is solved by the following technical solutions:
A method for three-dimensional electrode electrolysis process high-concentration ammonia nitrogenous wastewater, is characterized in that comprising the following steps:
1) three-dimensional electrode electrolysis reaction treatment: high-concentration ammonia nitrogenous wastewater three-dimensional electrode electrolysis device is processed, in described three-dimensional electrode electrolysis device, granule electrode used is the particle granules made with ferrum-based catalyst be filled between cathode-anode plate, and current density is 20 ~ 90A/m
2, electrolysis time is 30 ~ 120min; Wherein said three-diemsnional electrode positive plate is titanizing steel plate, and negative plate is steel plate; The iron-carbon ratio example of the particle granules of granule electrode is 1 ~ 6, and preferred size is 0.5 ~ 3cm, and loading level is 70 ~ 80%;
2) flocculation reaction process: the water outlet of three-dimensional electrode electrolysis reaction treatment enters flocculation tank, carries out dosing flocculation reaction process, adds sodium hydroxide, pH to 8 ~ 9 of adjustment waste water, and reacting treatment time is 10 ~ 30 minutes;
3) precipitin reaction process: after flocculation, water outlet enters in perpendicular stream reaction settling basin and carries out precipitation process, and the precipitin reaction time is 60 ~ 180 minutes;
4) clean water basin process: the water outlet of perpendicular stream reaction settling basin enters clean water basin, stores and discharges.
In technique scheme, preferred steps 1) NH of described pending high-concentration ammonia nitrogenous wastewater
3-N 2000 ~ 3000mg/L, pH<1;
Step 1) NH of described waste water after three-dimensional electrode electrolysis process
3-N 50 ~ 70mg/L, pH are 4 ~ 5;
Step 2) NH of described waste water after flocculation treatment
3-N 20 ~ 30mg/L, pH are 8 ~ 9.5;
Step 3) NH of described waste water after precipitation process
3-N<15mg/L, pH are 8 ~ 9.5.
Principle of the present invention: at present Based on Three-dimensional Electrode Method has 4 kinds of different viewpoints to organic mechanism of degradation: 1. produce extremely strong OH and H of oxidisability in three-dimensional electrode electrolysis process
2o
2, oxidation operation is decomposed; 2. form the extremely strong O of oxidisability in three-dimensional electrode electrolysis process simultaneously
3, role makes oxidation operation decompose; 3. partial organic substances on three-diemsnional electrode anode by direct oxidation; 4. more than, 3 kinds of effects have both at the same time, but not yet clear and definite to often kind of effect role size in organic matter degradation.In addition, also have viewpoint to think when there being chlorion to exist, the essential substance removing oxide compound is the hypochlorite that three-dimensional electrolysis produces.
The inventive method has the following advantages relative to prior art tool:
(1) in the three-dimensional electrode electrolysis device that the inventive method adopts, particle filled composite is sensed under the electric field action of high-gradient becomes polar particle, namely there is anodic reaction in particle one end, the other end generation cathodic reaction, and whole particle forms a three-dimensional electrode, form numerous micro cell between particle and particle, catalysis generates the free radical OH that can destroy pollutent structure.Meanwhile, in the electrocatalytic reaction of reactor, the O produced by electrolysis
2with the O that the external world provides
2on three-diemsnional electrode negative electrode, reduction produces H
2o
2.In addition, when in waste water, chloride ion content is higher, three-dimensional electrolysis can produce a large amount of hypochlorites.These materials all have strong oxidizing property, have higher removal effect to ammonia nitrogen.
(2) compared to traditional two-dimentional electrolysis, the inventive method adopts efficient iron-base catalyzer, significantly improves NH
3the clearance of-N.In addition, the present invention overcomes the defect that conventional two-dimensional electrolysis useful area is little, current efficiency is low, there is larger specific surface area, more excellent rate of mass transfer, oxidative degradation ability, can efficient, fast degradation ammonia nitrogen in high density.
(3) because waste water ph is low, according to other treatment processs, first need regulate waste water ph, and the present invention is without the need to adjust ph, and aftertreatment is simple.Simplify treatment scheme, reduce processing cost.
(4) the inventive method adopts three-dimensional electrode electrolysis appliance arrangement, and whole set process equipment is comparatively simple, compact, and floor space is few, sludge quantity is little, and granule electrode does not need manipulation of regeneration for a long time, and process cost is low, is easy to control, and is convenient to realize industrialization.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the method for a kind of three-dimensional electrode electrolysis process of the present invention high-concentration ammonia nitrogenous wastewater.
1 be wherein three-dimensional electrode electrolysis device in figure, 2 is flocculation tank, and 3 is perpendicular stream reaction settling basin, and 4 is clean water basin.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
By certain high ammonia-nitrogen wastewater, adopt the method for a kind of three-dimensional electrode electrolysis process of the present invention high-concentration ammonia nitrogenous wastewater.NH
3-N 2000 ~ 3000mg/L, pH are 0.82.First carry out three-dimensional electrode electrolysis process, anode is titanizing steel plate, and negative electrode is steel plate, and granule electrode particle is ferrum-based catalyst, is of a size of 2.0cm, and loading level is 75%, reaction 2h, now, and the waste water NH after three-dimensional electrode electrolysis process
3-N 51mg/L, pH are 4.5.Waste water after three-dimensional electrode electrolysis process carries out flocculation reaction, and the pH adding sodium hydroxide adjustment waste water is 9, reacts 15 minutes, now, and the waste water NH after flocculation treatment
3-N 25mg/L.Waste water after flocculation reaction dosing enters perpendicular stream reaction settling basin and precipitates, sedimentation time 60 minutes, the waste water NH after perpendicular stream reaction settling basin
3-N10mg/L, pH are 9, reach first discharge standard.
Embodiment 2
By certain high ammonia-nitrogen wastewater, adopt the method for a kind of three-dimensional electrode electrolysis process of the present invention high-concentration ammonia nitrogenous wastewater.NH
3-N 2000 ~ 3000mg/L, pH are 0.65.First carry out three-dimensional electrode electrolysis process, anode is titanizing steel plate, and negative electrode is steel plate, and granule electrode particle is ferrum-based catalyst, is of a size of 2.0cm, and loading level is 75%, reaction 2h, now, and the waste water NH after three-dimensional electrode electrolysis process
3-N 51mg/L, pH are 4.8.Waste water after three-dimensional electrode electrolysis process carries out flocculation reaction, and the pH adding sodium hydroxide adjustment waste water is 9, reacts 15 minutes, now, and the waste water NH after flocculation treatment
3-N 20mg/L.Waste water after flocculation reaction dosing enters perpendicular stream reaction settling basin and precipitates, sedimentation time 60 minutes, the waste water NH after perpendicular stream reaction settling basin
3-N8mg/L, pH are 9, reach first discharge standard.
Embodiment 3
By certain high ammonia-nitrogen wastewater, adopt the method for a kind of three-dimensional electrolysis process of the present invention high-concentration ammonia nitrogenous wastewater.NH
3-N 2000 ~ 3000mg/L, pH are 0.78.First carry out three-dimensional electrode electrolysis process, anode is titanizing steel plate, and negative electrode is steel plate, and granule electrode particle is ferrum-based catalyst, is of a size of 2.0cm, and loading level is 75%, reaction 2h, now, and the waste water NH after three-dimensional electrode electrolysis process
3-N 51mg/L, pH are 5.2.Waste water after three-dimensional electrode electrolysis process carries out flocculation reaction, and the pH adding sodium hydroxide adjustment waste water is 9, reacts 15 minutes, now, and the waste water NH after flocculation treatment
3-N 21mg/L.Waste water after flocculation reaction dosing enters perpendicular stream reaction settling basin and precipitates, sedimentation time 60 minutes, the waste water NH after perpendicular stream reaction settling basin
3-N12mg/L, pH are 9, reach first discharge standard.
Embodiment 4
By certain high ammonia-nitrogen wastewater, adopt the method for a kind of three-dimensional electrolysis process of the present invention high-concentration ammonia nitrogenous wastewater.NH
3-N 2000 ~ 3000mg/L, pH are 0.66.First carry out three-dimensional electrode electrolysis process, anode is titanizing steel plate, and negative electrode is steel plate, and ion electrode particle is ferrum-based catalyst, is of a size of 2.0cm, and loading level is 75%, reaction 2h, now, and the waste water NH after three-dimensional electrode electrolysis process
3-N 51mg/L, pH are 5.6.Waste water after three-dimensional electrode electrolysis process carries out flocculation reaction, and the pH adding sodium hydroxide adjustment waste water is 9, reacts 15 minutes, now, and the waste water NH after flocculation treatment
3-N 23mg/L.Waste water after flocculation reaction dosing enters perpendicular stream reaction settling basin and precipitates, sedimentation time 60 minutes, the waste water NH after perpendicular stream reaction settling basin
3-N9mg/L, pH are 9, reach first discharge standard.
Claims (3)
1. a method for three-dimensional electrode electrolysis process high-concentration ammonia nitrogenous wastewater, is characterized in that comprising following operation steps:
1) three-dimensional electrode electrolysis reaction treatment: high-concentration ammonia nitrogenous wastewater three-dimensional electrode electrolysis device is processed, in described three-dimensional electrode electrolysis device, granule electrode used is the particle granules made with ferrum-based catalyst be filled between cathode-anode plate, and current density is 20 ~ 90A/m
2, electrolysis time is 30 ~ 120min;
Wherein said three-dimensional electrolysis pole plate anode is titanizing steel plate, and negative electrode is steel plate; The particle granules iron-carbon ratio example of granule electrode is 1 ~ 6;
2) flocculation reaction process: the water outlet of three-dimensional electrode electrolysis reaction treatment enters flocculation tank, carries out dosing flocculation reaction process, adds sodium hydroxide, the pH 8 ~ 9 of adjustment waste water, and reacting treatment time is 10 ~ 30 minutes;
3) precipitin reaction process: after flocculation reaction, water outlet enters in perpendicular stream reaction settling basin and carries out precipitation process, and the precipitin reaction time is 60 ~ 180 minutes;
4) clean water basin process: the water outlet of perpendicular stream reaction settling basin enters clean water basin, stores and discharges.
2. the method for a kind of three-dimensional electrode electrolysis process high-concentration ammonia nitrogenous wastewater according to claim 1, it is characterized in that: the particle granules of described granule electrode is of a size of 0.5 ~ 3cm, loading level is 70 ~ 80%.
3. the method for a kind of three-dimensional electrode electrolysis process high-concentration ammonia nitrogenous wastewater according to claim 1, is characterized in that: step 1) NH of described pending high-concentration ammonia nitrogenous wastewater
3-N 2000 ~ 3000mg/L, pH<1;
Step 1) NH of described waste water after three-dimensional electrode electrolysis process
3-N 50 ~ 70mg/L, pH are 4 ~ 5;
Step 2) NH of described waste water after flocculation treatment
3-N 20 ~ 30mg/L, pH are 8 ~ 9.5;
Step 3) NH of described waste water after precipitation process
3-N<15mg/L, pH are 8 ~ 9.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830210A (en) * | 2017-03-07 | 2017-06-13 | 南昌大学 | A kind of three-diemsnional electrode couples iron-carbon micro-electrolysis sewage disposal system |
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| CN101955300A (en) * | 2010-08-31 | 2011-01-26 | 中国矿业大学(北京) | Coke powder bipolar three-dimensional electrode water treatment reactor |
| CN103193301A (en) * | 2013-04-27 | 2013-07-10 | 国电环境保护研究院 | Electrochemical reactor for processing nitrogenous organic wastewater, and application and processing method thereof |
| CN104016547A (en) * | 2014-06-19 | 2014-09-03 | 中冶建筑研究总院有限公司 | Advanced treatment and zero emission process for coking wastewater |
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Patent Citations (5)
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|---|---|---|---|---|
| CN101434443A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Method and apparatus for treating oil refining sewerage |
| CN101781054A (en) * | 2010-02-11 | 2010-07-21 | 南京大学 | Method for utilizing three-dimensional electrode coagulation combination to carry out advanced treatment on coking wastewater |
| CN101955300A (en) * | 2010-08-31 | 2011-01-26 | 中国矿业大学(北京) | Coke powder bipolar three-dimensional electrode water treatment reactor |
| CN103193301A (en) * | 2013-04-27 | 2013-07-10 | 国电环境保护研究院 | Electrochemical reactor for processing nitrogenous organic wastewater, and application and processing method thereof |
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| CN106830210A (en) * | 2017-03-07 | 2017-06-13 | 南昌大学 | A kind of three-diemsnional electrode couples iron-carbon micro-electrolysis sewage disposal system |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
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Effective date of registration: 20161011 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant before: CNOOC Energy Development Co., Ltd. |
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