CN101746871A - Electrochemical method for removing nitrate from drinking water source - Google Patents
Electrochemical method for removing nitrate from drinking water source Download PDFInfo
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- CN101746871A CN101746871A CN200810239271A CN200810239271A CN101746871A CN 101746871 A CN101746871 A CN 101746871A CN 200810239271 A CN200810239271 A CN 200810239271A CN 200810239271 A CN200810239271 A CN 200810239271A CN 101746871 A CN101746871 A CN 101746871A
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Abstract
The invention relates to an electrochemical method for removing nitrate from a drinking water source. In the invention, the method comprises a step of electrolyzing the water to be treated for 1 to 5 hours at a current density of between 10 and 50 mA/cm<2> by using an electrode containing Fe, Ti, Al, Pd, Cu, Zn, Sn, Cu/Zn, Cu/Pd or Ti/Pd as a cathode and using an insoluble electrode containing Pt, Ir, Ru, Pd or Pb as an anode in an electrolytic bath. The method of the invention also comprises a step of adding an ionic compound of chlorine in the electrolytic process. The electrochemical method reduces the cost of the electrochemical reduction of the nitrate and improves the treatment efficiency, so the practicability of removing the nitrate from the drinking water by the electrochemical method is improved.
Description
Technical field
The invention belongs to the Application Areas of water technology, specifically relate to the method that a kind of electrochemistry is removed nitrate in the drinking water source.
Background technology
At present, the underground water of many countries all is subjected to azotate pollution in various degree.Some areas in Europe, the pollution of nitrate has just reached more serious level before 30 years, but also is continuing growth.In China, groundwater azotate pollution is also ubiquitous, and regional situation densely populated and the grain high yield is particularly serious.At the initial stage eighties, the underground water in some cities of China just is subjected to azotate pollution, the monitoring data in 41 cities is shown at that time in existing 1/3 the urban groundwater to have the azotate pollution problem, and some local pollution controls are very serious.The underground water of drinking high nitrate content can work the mischief to human health, nitrate to the harm of human body mainly be since its to be reduced to nitrite in human body caused, this reductive action occurs in the digestive tube of saliva neutralization less than three months babies of any age bracket human body.Nitrite can cause methemoglobinemia and bring out multiple cancer, also there is detrimentally affect in human vas nerve and cardiovascular systems when heavy dose of.The World Health Organization's current standards was formulated in 1984, and its directive standard to nitrate nitrogen content in the tap water is 10mg/L, and proposed standard is 5mg/L.The standard of the U.S. is 10m g/L, and new " drinking water sanitary standard " that China came into effect from July, 2007 stipulates that also nitrate nitrogen must not surpass 10mg/L in the tap water.
At present, mainly contain the compound integrated method of physics method, chemical method, biological process and these technology to the purification techniques of the tap water that is subjected to azotate pollution.Physical treatment process does not carry out reduction decomposition to nitrate, so the shortcoming of this technology maximum is exactly the handling problems that has waste liquid, deals with improperly and can cause second environmental pollution.Method of chemical treatment mainly is a catalytic reduction method, this method is difficult to nitrate is reduced into harmless nitrogen fully, and can produce reaction product such as metal ion, metal oxide or hydrated metal oxide and cause secondary pollution, so subsequent disposal is had relatively high expectations.Present biological denitrification method is because the nutritive deficiency in the underground water need to be added organic carbon sources such as methyl alcohol, but shortcoming such as low, the anti-load impact ability of ubiquity processing efficiency is weak.
By comparison, electrochemical process is utilized the redox reaction partner of electronics as cleaning, directly or indirectly carries out the conversion between chemical substance, does not need to widely apply oxygenant or reductive agent as chemical method, thereby is a kind of method of comparatively environmental protection.As disclosed method in Japanese Patent JP2003-71461A,, thereby and then utilize chemical catalysis that the ammonia nitrogen that generates is oxidized to the purpose that harmless nitrogen reaches removal nitrate earlier with nitrate reduction ammonification or other gaseous nitrogen compounds.Disclose in Chinese patent CN1789498A and used the metal modified active carbon fiber electrode and remove the method for nitrate with this electrode, still this method can not removed nitrate reduction by product (mainly being ammonium salt).At document: Feng etc., Journal of Hazardous Materials, Volume 103, pp 65-78; Among the JP2006-68743A, also disclose the research that utilizes the ammonia nitrogen in the electrochemical process oxidized waste water, also failed to solve the problem of by product nitrate removal.Therefore, ubiquity has generated by products such as nitrite and ammonia when removing nitrate because electrochemical process is reduced, thereby has caused other pollution, and never has effective solution up to now, has limited the practicability of electrochemical process.
Summary of the invention
The objective of the invention is to overcome basically the many disadvantages of existing electrochemical process, thereby provide a kind of innoxious ground to remove the electrochemical method of nitrate in the drinking water source fully.Method of the present invention can be removed by product nitrite and the ammonia that generates effectively in an electrochemical reaction groove, and make nitrate all be converted into the nitrogen of environmental sound, thereby reach the purpose of innoxious removal nitrate in a single reactor, and need not other auxiliary treatment unit.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of electrochemistry and remove the method for nitrate in the drinking water source, comprise following step: in an electrolyzer, use to comprise Fe, Ti, Al, Pd, Cu, Zn, Sn, Cu/Zn, the electrode of Cu/Pd or Ti/Pd use to comprise Pt as negative electrode, Ir, Ru, the insoluble electrode of Pd or Pb system be as anode, with pending water at current density 10-50mA/cm
2Down, electrolysis 1-5 hour.
Method of the present invention is applicable to handles NO
3 -N concentration is the water of 25-100mg/L.
Electrochemistry provided by the invention is removed the method for nitrate in the drinking water source, also is included in the electrolytic process, adds the chlorion compound.
Preferred sodium-chlor of described chlorion compound or Repone K.
The addition of described chlorion compound is 0-5g/L (a pending water), and preferred addition is 0.3-1.0g/L.
The interpolation of described chlorion compound is preferably added after electrolysis begins 0.5-1.5 hour.
In one embodiment of the invention, negative electrode is Cu/Zn or Cu/Pd, and preferred anode is Ti/RuO
2, Ti/IrO
2, Ti/Pt or Ti/Pt-IrO
2
In one embodiment of the invention, described electrolyzer is cylindrical or cubic cylindricality.
In one embodiment of the invention, described electrolyzer is single flute profile formula.
In one embodiment of the invention, the multiple-grooved form of described electrolyzer for separating with the macroion exchange membrane.
In specific embodiments of the present invention, the shape of electrode can be the various arbitrary shapes of determining according to actual needs such as tabular, netted, round shape or wire.
The principle that method of the present invention can all be removed nitrate is: nitrate obtains electronics at negative electrode and is reduced generation nitrogen, nitrite or ammonia; Simultaneously, the nitrite of generation or ammonia are nitrogen or nitrate by anodic oxidation, pass through successive reduction-oxidation process like this between negative electrode and anode, and the nitrate in the water all is converted into harmless nitrogen, thereby reaches the purposes that nitrate is all removed.
The present invention is in electrolytic process, according to the drinking-water quality situation, can add the chloride ion-containing compound in right amount (if when the object of handling is the brackish water water source, because it has contained enough chlorions, then can not need additionally to add chlorion), to improve the removal efficient of nitrate.This is because under the situation that chlorion exists, and at negative electrode with the complete reductive of nitrate simultaneously, the hypochlorite that produces at anode electrolysis can carry out oxidation to by product.
Method of the present invention can be removed nitrate fully, and the reaction formula in its process is as follows:
Near the negative electrode:
NO
3 -+H
2O+2e
-＝NO
2 -+2OH
- (1)
NO
3 -+3H
2O+5e
-＝1/2N
2+6OH
- (2)
NO
2 -+5H
2O+6e
-＝NH
3+7OH
- (3)
2NO
2 -+4H
2O+6e
-＝N
2+8OH
- (4)
2H
2O+2e
-=H
2+ 2OH
-(side reaction) (5)
Near the anode:
2Cl
-→Cl
2+2e
- (6)
Cl
2+H
2O→HClO+H
++Cl
- (7)
HClO→ClO
-+H
+ (8)
NH
4 ++HClO→N
2+H
2O+H
++Cl
- (9)
NO
2 -+HClO→NO
3 -+H
2O+Cl
- (10)
Compared with prior art, characteristics of the present invention are:
(1) all processing all can be finished in single reaction unit, need not other reactors;
(2) electrochemical reaction among the present invention is removed nitrate efficient height, can be with the generation of whole removals of nitrate and no coupling product;
(3) through after the method for the present invention, effluent quality is good, and anti-load change ability is strong; Do not need settler, can save the secondary treatment cost;
(4) be used for implementing electrochemistry of the present invention remove the reactor of the method for drinking water source nitrate make simple, easy to operate, the level of automation height;
(5) the present invention also is applicable to the processing that is subjected to azotate pollution underground water or other water source except that the removal that is used for tap water nitrate, for example can be used for the removal fully of ammonia-state nitrogen in the water.
In sum, the present invention has reduced the cost of electrochemical reduction nitrate, has improved processing efficiency, thereby has improved the practicality that electrochemical process is removed tap water nitrate fully.
Description of drawings
Fig. 1 implements the synoptic diagram that electrochemistry of the present invention is removed a kind of reaction unit of the method for nitrate in the drinking water source;
Fig. 2 implements the synoptic diagram that electrochemistry of the present invention is removed a kind of reaction unit of the method for nitrate in the drinking water source;
Fig. 3 implements the skeleton view that electrochemistry of the present invention is removed a kind of reaction unit of the method for nitrate in the drinking water source;
Wherein: 1-direct supply, 2-anode, 3-negative electrode, 4-electrolyzer, 5-magnetic stirring apparatus, 6-recycle pump, 7-circulation groove, 8-water outlet, 9-water-in.
Embodiment
In the device as shown in Figure 1, electrolyzer is that a volume is the cylindrical tank of 500mL, is made by polyethylene, and negative electrode is Cu/Zn (Cu:62.2wt%; Zn:37.8wt%) wire electrode, anode are Ti/Pt-IrO
2Wire electrode, a direct current stabilizer are as power supply, and its virtual voltage is 0-50V, and watt current is 0-5A.Each electrolytic nitrate solution volume is 400mL, and effective usable floor area of electrode is 50cm
2
In the experiment with synthetic azotate pollution water (NO
3 --N, 50mg/L; Na
2SO
40.5g/L NaCl0.5g/L) 400mL puts in the electrolyzer, power-on is regulated electric current, and making current density is 40mA/cm
2React after 5 hours, water outlet nitrate nitrogen concentration is 6.5mg/L; Nitrite and ammonia nitrogen all do not detect, and meet national drinking water standard.
Remove the method such as the example 1 of nitrate in the water, but nitrate nitrogen in underground water concentration is increased to 100mg/L, reacts after 5 hours, water outlet nitrate nitrogen concentration is 9.7mg/L; Nitrite and ammonia nitrogen all do not detect, and meet national drinking water standard.
As shown in Figures 2 and 3, electrolyzer (reactor) is a 2cm x 13cm x 5.2cm=135.2cm
3The rectangular parallelepiped tank, make by polyethylene, negative electrode is Cu/Zn (Cu:62.2wt%; Zn:37.8wt%) plate electrode, anode are Ti/Pt-IrO
2Plate electrode, negative electrode place electrolyzer central authorities, and anode places the negative electrode both sides.A direct current stabilizer is as power supply, and its virtual voltage is 0-50V, and watt current is 0-5A.Each electrolytic nitrate solution volume is 1L, and effective usable floor area of electrode is 10cm x 13cm=130cm
2Make liquid circulation between circulation groove and the reactor by recycle pump in the electrolytic process.
In the experiment with synthetic azotate pollution water (NO
3 --N, 25mg/L; Na
2SO
40.5g/L NaCl0.5g/L) 1L puts in the circulation groove, power-on is regulated electric current, and making current density is 1O mA/cm
2React after 1.5 hours, water outlet nitrate nitrogen concentration is 8.3mg/L; Nitrite and ammonia nitrogen all do not detect, and meet national drinking water standard.
Remove the method such as the example 3 of nitrate in the water, underground water NO
3 --N is 50mg/L, Na
2SO
40.5g/L current density is 10mA/cm
2After electrolysis time is 1.5 hours, add the NaCl of 0.5g/L in circulation groove, electrolytic reaction is after 2 hours, and water outlet nitrate nitrogen concentration is 9.4mg/L; Nitrite and ammonia nitrogen all do not detect, and meet national drinking water standard.
Claims (10)
1. an electrochemistry is removed the method for nitrate in the drinking water source, comprising: in an electrolyzer, use to comprise Fe, Ti, Al, Pd, Cu, Zn, Sn, Cu/Zn, the electrode of Cu/Pd or Ti/Pd use to comprise Pt as negative electrode, Ir, Ru, the insoluble electrode of Pd or Pb system be as anode, with pending water at current density 10-50mA/cm
2Down, electrolysis 1-5 hour.
2. electrochemistry according to claim 1 is removed the method for nitrate in the drinking water source, it is characterized in that: the NO in the described pending water
3 -N concentration is 25-100mg/L.
3. electrochemistry according to claim 1 is removed the method for nitrate in the drinking water source, it is characterized in that: also be included in the electrolytic process, add the chlorion compound.
4. electrochemistry according to claim 3 is removed the method for nitrate in the drinking water source, and it is characterized in that: described chlorion compound is sodium-chlor or Repone K.
5. according to the method for nitrate in claim 3 or the 4 described electrochemistry removal drinking water sources, it is characterized in that: the addition of described chlorion compound is the pending water of 0.3-5g/L.
6. electrochemistry according to claim 5 is removed the method for nitrate in the drinking water source, and it is characterized in that: the addition of described chlorion compound is the pending water of 0.3-1.0g/L.
7. according to the method for nitrate in claim 3 or the 4 described electrochemistry removal drinking water sources, it is characterized in that: the electrolysis that is added on of described chlorion compound begins to add after 0.5-1.5 hour.
8. electrochemistry according to claim 1 is removed the method for nitrate in the drinking water source, and it is characterized in that: described negative electrode is Cu/Zn or Cu/Pd, and anode is Ti/RuO
2, Ti/IrO
2, Ti/Pt or Ti/Pt-IrO
2
9. according to the method for nitrate in claim 1 or the 3 described electrochemistry removal drinking water sources, it is characterized in that: described electrolyzer is cylindrical or cubic cylindricality.
10. according to the method for nitrate in claim 1 or the 3 described electrochemistry removal drinking water sources, it is characterized in that: the multiple-grooved form of described electrolyzer for separating with the macroion exchange membrane.
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|---|---|---|---|
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| CN104817142A (en) * | 2015-04-24 | 2015-08-05 | 青岛双瑞海洋环境工程股份有限公司 | Electrochemical method and device for removing nitrate in wastewater |
| CN106365261A (en) * | 2016-11-18 | 2017-02-01 | 北京化工大学 | Electrode for synchronously removing nitrate and tetrachloromethane from water and preparation method and use method thereof |
| CN109264834A (en) * | 2018-11-05 | 2019-01-25 | 中国地质大学（北京） | A kind of processing method and reactor of the nitrogenous organic wastewater with difficult degradation thereby containing chlorine |
| CN109650496A (en) * | 2019-01-28 | 2019-04-19 | 江苏融汇环境工程有限公司 | The method of electrocatalytic oxidation processing rubber and plastic waste water |
| TWI675804B (en) * | 2018-12-18 | 2019-11-01 | 國立中山大學 | Method for removing ammonia nitrogen in aqueous solution |
| CN110760922A (en) * | 2019-10-30 | 2020-02-07 | 昆山金易得环保科技有限公司 | Tin stripping liquid, method for removing tin-containing layer on substrate and method for recovering tin |
| CN110803812A (en) * | 2019-12-13 | 2020-02-18 | 碳能科技（北京）有限公司 | High-salinity high-nitrate industrial wastewater treatment method and system |
| CN111170416A (en) * | 2020-01-09 | 2020-05-19 | 中国原子能科学研究院 | Method for removing nitric acid in nitric acid-containing solution |
| US10882767B2 (en) | 2018-12-18 | 2021-01-05 | National Sun Yat-Sen University | Method for removing ammonia nitrogen in aqueous solution |
| CN113371796A (en) * | 2021-06-22 | 2021-09-10 | 中石化南京化工研究院有限公司 | Method for removing nitrate nitrogen through catalytic electrolysis of Cu/Zn electrode |
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| FR2860784B1 (en) * | 2003-10-08 | 2007-12-07 | Cooperative Agricole Des Perri | PROCESS FOR THE CHEMICAL TREATMENT OF A LIQUID MEDIUM CHARGED WITH NITRATE, DEVICE FOR TREATING SUCH A LIQUID MEDIUM AND. |
| CN100366552C (en) * | 2005-11-10 | 2008-02-06 | 复旦大学 | Process for depth treating total nitrogen of urban sewage |
| CN100579922C (en) * | 2006-12-08 | 2010-01-13 | 辽宁科技大学 | Energy-saving process for treating high ammonia nitrogen waste water |
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| CN104817142A (en) * | 2015-04-24 | 2015-08-05 | 青岛双瑞海洋环境工程股份有限公司 | Electrochemical method and device for removing nitrate in wastewater |
| CN106365261A (en) * | 2016-11-18 | 2017-02-01 | 北京化工大学 | Electrode for synchronously removing nitrate and tetrachloromethane from water and preparation method and use method thereof |
| CN109264834A (en) * | 2018-11-05 | 2019-01-25 | 中国地质大学（北京） | A kind of processing method and reactor of the nitrogenous organic wastewater with difficult degradation thereby containing chlorine |
| US10882767B2 (en) | 2018-12-18 | 2021-01-05 | National Sun Yat-Sen University | Method for removing ammonia nitrogen in aqueous solution |
| TWI675804B (en) * | 2018-12-18 | 2019-11-01 | 國立中山大學 | Method for removing ammonia nitrogen in aqueous solution |
| CN109650496A (en) * | 2019-01-28 | 2019-04-19 | 江苏融汇环境工程有限公司 | The method of electrocatalytic oxidation processing rubber and plastic waste water |
| CN110760922B (en) * | 2019-10-30 | 2021-08-17 | 昆山金易得环保科技有限公司 | Tin stripping liquid, method for removing tin-containing layer on substrate and method for recovering tin |
| CN110760922A (en) * | 2019-10-30 | 2020-02-07 | 昆山金易得环保科技有限公司 | Tin stripping liquid, method for removing tin-containing layer on substrate and method for recovering tin |
| CN110803812A (en) * | 2019-12-13 | 2020-02-18 | 碳能科技（北京）有限公司 | High-salinity high-nitrate industrial wastewater treatment method and system |
| CN111170416A (en) * | 2020-01-09 | 2020-05-19 | 中国原子能科学研究院 | Method for removing nitric acid in nitric acid-containing solution |
| CN114106343A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Preparation method of metal organic framework material |
| CN113371796A (en) * | 2021-06-22 | 2021-09-10 | 中石化南京化工研究院有限公司 | Method for removing nitrate nitrogen through catalytic electrolysis of Cu/Zn electrode |
| CN114702108A (en) * | 2022-03-25 | 2022-07-05 | 方义 | Electrolytic device and method for removing nitrogen from industrial wastewater |
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