CN104944531B - A kind of method that Ti nano-electrodes efficiently remove nitrate in groundwater - Google Patents
A kind of method that Ti nano-electrodes efficiently remove nitrate in groundwater Download PDFInfo
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Abstract
A kind of method that Ti nano-electrodes efficiently remove nitrate in groundwater, step are as follows：1st, azotate pollution water is taken, wherein nitrate nitrogen content is 25～100mg/L, 0.1～1.0g/L of sodium sulphate content；2nd, adopt with RuO2+IrO2Mesh electrode is to aid in the Ti nano-electrodes of electrode fabrication to be negative electrode, adopts Ti/Pt electrodes for anode, negative electrode and plate 5～20mm of spacing；3rd, azotate pollution water, negative electrode and anode are put in electrolysis bath, setting electric current is electrolysed 60～300 minutes, so as to reduce removal nitrate under the conditions of 0.2～3.0A；Nitrate obtains electronics in negative electrode and is reduced generation nitrogen, nitrite or ammonia, reaches the purpose for removing nitrate；The present invention uses RuO2+IrO2The Ti nano-electrodes that mesh electrode is made as auxiliary electrode, effectively remove nitrate, in an electrochemical reaction groove without the need for the processing meanss that other aid in.
Description
Technical field
The invention belongs to nitrate processing technology field in water, particularly relates to a kind of Ti nano-electrodes efficiently removably
The method of nitrate in lower water.
Background technology
In recent years, with the growth and the progress of social economy of population, the pollution of nitrate in water is on the rise.In Europe
Some areas, the pollution of nitrate before 30 years just reached than more serious level, but also continuing growth.At present, I
The subsoil water of state's most area it is different degrees of by azotate pollution, indivedual its concentration of area are even more than 100mg-N/
L.The excessive nitrate of intake has many harm to health, is such as converted into Hb A hemoglobin adult in human body and do not possess oxygen
The metahemoglobin of transport capacity, causes methemoglobinemia, can cause death when serious；During nitrate transformation
Inferior ammonium nitrate of generation etc. has carcinogenic, teratogenesis and mutagenic action, can induce various tumor diseases.World Health Organization (WHO)
(WHO)《Water quality standard for drinking water》And China《Drinking water sanitary standard》All specify that nitrate nitrogen highest limit value is 10mg/
L。
The method of nitrate in eliminating water is gone mainly to have Physical, bioanalysises and chemical method etc. at present.Physical is simply by nitre
During hydrochlorate is transferred to other media from water or become concentrated solution, fundamentally do not remove nitrate, the concentration after transfer
Liquid, if dealing with improperly, can cause secondary pollution to environment.Biological denitrification method is to be by nitrate transformation by microbial action
Nitrogen, is a kind of most commonly used nitrate removal method of current practice.But reactor volume needed for which is huge, cost of erection
With height, and process cycle is general longer, easily receives the environmental factorss such as condition such as temperature, pH value, pollutant levels and dissolved oxygen concentration
Impact.Chemical reduction method is mainly catalytic reduction method, most of nitrate nitrogen can be converted into nitrogen effectively, but be reacted
Required hydrogen property is active, expensive, is not easy to storage transport, and operating condition (pH value, the water required for catalytic reduction method
Matter, mass-transfer efficiency etc.) it is difficult to control to so that the method is subject to many limitations in actual applications.
By comparison, electrochemical process participates in thing as clean redox reaction by the use of electronics, directly or indirectly enters
Nitrate nitrogen is reduced into environment amenable nitrogen, clearance height, effect stability, handling by the conversion between row chemical substance
Paid close attention to by more and more scholars with low, easy to control.The research that nitrate is reduced with regard to electrochemical process has had many documents
Reported, the patent of the method for nitrate in drinking water source was also removed using different anode and cathode united application electrochemical processes；Gold
The patent of category modified active carbon fiber electrode and the method with electrode removal nitrate, but all fail to solve electrochemical reduction
The by-product problem such as the nitrite produced during nitrate and ammonia, it is practical so as to limit which.With regard to nano-electrode
Making has had many researchs, and in the manufacturing process of nano-electrode, does not also find using noble metal RuO2As auxiliary electricity
Pole is negative electrode making the research of nano-electrode, and the nano-electrode with regard to making of the method removes the research mesh of nitrate in eliminating water
It is front yet not have been reported that.
The content of the invention
For the problem for overcoming above-mentioned prior art to exist, it is an object of the invention to provide a kind of Ti nano-electrodes are efficient
The method for removing nitrate in groundwater, using RuO2+IrO2The Ti nano-electrodes that mesh electrode is made as auxiliary electrode,
Nitrate is removed effectively in one electrochemical reaction groove, without the need for the processing meanss that other aid in.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of method that Ti nano-electrodes efficiently remove nitrate in groundwater, using with RuO2+IrO2Supplemented by mesh electrode
The Ti nano-electrodes of electrode fabrication are helped, and nitrate are effectively removed in an electrolysis bath, without the need for the processing meanss that other aid in,
Specifically include following steps：
Step 1：Take azotate pollution water, wherein nitrate nitrogen content is 25～100mg/L, sodium sulphate content 0.1～
1.0g/L；
Step 2：Adopt with RuO2+IrO2It is negative electrode that mesh electrode is the Ti nano-electrodes of auxiliary electrode fabrication, using Ti/
Pt electrodes are anode, negative electrode and plate 5～20mm of spacing；
Step 3：Azotate pollution water, negative electrode and anode are put in electrolysis bath, setting electric current is in 0.2～3.0A conditions
Under, it is electrolysed 60～300 minutes, so as to reduce removal nitrate；Nitrate obtains electronics in negative electrode and is reduced generation nitrogen, nitrous
Hydrochlorate or ammonia, reach the purpose for removing nitrate；Reaction equation is as follows：
Cathode reaction：
NO3 -+H2O+2e-=NO2 -+2OH- (1)
NO3 -+3H2O+5e-=1/2N2+6OH- (2)
NO2 -+5H2O+6e-=NH3+7OH- (3)
2NO2 -+4H2O+6e-=N2+8OH- (4)
2H2O+2e-=H2+2OH-(side reaction) (5)
It is described with RuO2+IrO2Mesh electrode is that the manufacture method of the Ti nano-electrodes for aiding in electrode fabrication is as follows：
(1) with the sand papering Ti pole plates of 100～180 mesh；
(2) by the Ti pole plates polished, deionized water is cleaned by ultrasonic 20～40 minutes；
(3) the Ti pole plates after ultrasonic cleaning are dried up stand-by；
(4) electrode is processed using constant pressure anodizing, the power supply that anodic oxidation is adopted is for D.C. regulated power supply；Specifically
For：Using RuO2+IrO2Mesh electrode is negative electrode for auxiliary electrode, and the Ti pole plates after adopting step 3 to dry up are working electrode i.e. sun
Pole, with containing the NH that mass percent is 0.01～0.30%4The aqueous solution of F makees electrolyte, in the 10～60V of oxidation voltage of setting
Under the conditions of, aoxidize 30～180 minutes；Microcosmic nano tube structure can be formed on the surface of anode, its electrode surface nanotube is formed
Principle be：1) in the presence of electric field, the water power near anode surface is from generation O2-, while titanium quickly dissolves, produce a large amount of
Ti4+, with O2-It is rapid to react, the oxidation titanium barrier layer of densification is formed in Ti polar board surfaces, it is main that following reaction occurs：
H2O→2H++O2- (1)
Ti-4e→Ti4+ (2)
Ti4++2O2-→TiO2 (3)
2) F in electrolyte solution-In the presence of electric field, migrate to anode, with oxidation titanium barrier layer generationization
Act on the TiF to form solubility6 2-, cause oxidation titanium barrier layer to form irregular indenture；With the prolongation of oxidization time,
Indenture is developing progressively hole core, and hole core becomes aperture because field makes peace chemical dissolution procedure again, and the density of aperture is continuously increased, most
After be evenly distributed on polar board surface and form ordered structure, the main reaction that occurs is：
TiO2+6F-+4H+→TiF6 2-+2H2O (4)
3) when aoxidizing titanium barrier layer and being equal with the dissolution velocity of bottom hole oxide layer to the speed that titanium substrate is advanced, the length in hole
Degree is not further added by, and ultimately forms independent orderly nano tube structure.
(5) the Ti pole plates with nanotube pattern for being formed are taken out after the completion of question response, after deionized water is cleaned by ultrasonic,
Re-dry obtains finished product Ti nano-electrodes.
The cylindrically shaped or cubic cylindricality of the electrolysis bath described in step 3, is handed over macroion between anode and negative electrode
Change film to separate, make electrolysis bath become multiple-grooved form；Or macroion exchange membrane is not placed between anode and negative electrode, make electrolysis bath into
For single cavity form.
Compared to the prior art compared with, the invention has the advantages that：
1) all process are completed in single reaction unit.
2) adopt RuO2+IrO2Mesh electrode makees the Ti nano-electrodes of auxiliary electrode making, in electrolytic process, electrode table
Face can form double electrical layerses and can fully adsorb nitrate ion, nitrate ion is more fully contacted with electrode surface, from
And efficient electroreduction removes nitrate.
3) removing nitrate efficiency ratio using Ti nano-electrodes uses Ti negative electrodes high, can efficiently go nitrate and nothing in eliminating water
The generation of by-product.
4) reactor makes and is simple and convenient to operate, low cost.
Description of the drawings
Fig. 1 is electrochemical reduction nitrate installation drawing.
Fig. 2 is Different electrodes in embodiment 1 to nitrate treatment effect.
Fig. 3 is Different electrodes in embodiment 2 to nitrate treatment effect.
Specific embodiment
Embodiment 1
As shown in figure 1, electrolysis bath is a cylindrical tank, it is made up of polythene material, a direct current stabilizer conduct
Power supply, its active voltage are 0～100V, and effective current is 0～5A.
By the azotate pollution water (NO of synthetic in experiment3 -- N, 50mg/L；Na2SO4, 0.5g/L) and 300mL is put into electricity
In solution groove, power-on adjusts electric current, makes electric current be 0.75A.Negative electrode and plate size are 15 × 5cm, pole plate
Effective area is 50.0cm2, anode use Ti/Pt electrodes, the negative electrode for 1. using be Ti negative electrodes, then react 90 minutes after nitric acid
Salt nitrogen concentration is down to 46.0mg/L from 50.0mg/L；2. negative electrode adopts the Ti nano-electrodes for making auxiliary electrode making with Ti electrodes
(Ti-Nano1) after, then reacting 90 minutes, nitrate nitrogen concentration drops to 42.0mg/L from 50.0mg/L, and removal rate ratio uses Ti
Electrode improves 100%；3. negative electrode is RuO2+IrO2Mesh electrode makees the Ti nano-electrodes (Ti-Nano2) of auxiliary electrode making,
After then reacting 90 minutes, nitrate nitrogen concentration is down to 29.1mg/L from 50.0mg/L, and removal rate ratio is improve using Ti electrodes
423%, the removal efficiency of nitrate is greatly improved, as a result as shown in Figure 2.
Embodiment 2
Electrolysis bath used by experiment and the method such as example 1 using nano-electrode removal nitrate, except that taking in experiment
Nitrate sewage 100mL, wherein NO3 -- N, 50mg/L；Na2SO4, 0.5g/L, adopt the size of negative electrode and plate for
10.0 × 2.5cm, pole plate effective area are 20cm2, under the conditions of current intensity is 0.75A, the negative electrode for 1. using is Ti negative electrodes,
After then reacting 60 minutes, nitrate nitrogen concentration is down to 47.5mg/L from 50.0mg/L；2. negative electrode is adopted and makees auxiliary electrode with Ti electrodes
The Ti nano-electrodes (Ti-Nano1) of making, then after reacting 60 minutes, nitrate nitrogen concentration drops to 36.0mg/L from 50.0mg/L,
Removal rate ratio improves 46% using Ti electrodes；3. negative electrode is RuO2+IrO2Mesh electrode makees the Ti nanometers of auxiliary electrode making
Negative electrode (Ti-Nano2), then after reacting 60 minutes, nitrate nitrogen concentration is down to 8.5mg/L from 50.0mg/L, and removal rate ratio is used
Ti electrodes improve 156%, greatly improve the removal efficiency of nitrate, as a result as shown in Figure 3.
Claims (2)
1. a kind of method that Ti nano-electrodes efficiently remove nitrate in groundwater, it is characterised in that：Using with RuO2+IrO2Net
Shape electrode is the Ti nano-electrodes for aiding in electrode fabrication, in an electrolysis bath effectively removes nitrate, without the need for other auxiliary
Processing meanss, specifically include following steps：
Step 1：Azotate pollution water is taken, wherein nitrate nitrogen content is 25～100mg/L, 0.1～1.0g/L of sodium sulphate content；
Step 2：Adopt with RuO2+IrO2It is negative electrode that mesh electrode is the Ti nano-electrodes of auxiliary electrode fabrication, electric using Ti/Pt
Extremely anode, negative electrode and plate 5～20mm of spacing；
Step 3：Azotate pollution water, negative electrode and anode are put in electrolysis bath, setting electric current is under the conditions of 0.2～3.0A, electric
Solution 60～300 minutes, so as to reduce removal nitrate；Nitrate obtains electronics in negative electrode and is reduced generation nitrogen, nitrite
Or ammonia, reach the purpose for removing nitrate；Reaction equation is as follows：
Cathode reaction：
NO3 -+H2O+2e-=NO2 -+2OH- (1)
NO3 -+3H2O+5e-=1/2N2+6OH- (2)
NO2 -+5H2O+6e-=NH3+7OH- (3)
2NO2 -+4H2O+6e-=N2+8OH- (4)
2H2O+2e-=H2+2OH-Side reaction (5)
It is described with RuO2+IrO2Mesh electrode is that the manufacture method of the Ti nano-electrodes for aiding in electrode fabrication is as follows：
(1) with the sand papering Ti pole plates of 100～180 mesh；
(2) by the Ti pole plates polished, deionized water is cleaned by ultrasonic 20～40 minutes；
(3) the Ti pole plates after ultrasonic cleaning are dried up stand-by；
(4) electrode is processed using constant pressure anodizing, the power supply that anodic oxidation is adopted is for D.C. regulated power supply；Specially：Adopt
Use RuO2+IrO2Mesh electrode is negative electrode for auxiliary electrode, the Ti pole plates after adopting step (3) to dry up for working electrode i.e. anode,
With containing the NH that mass percent is 0.01～0.30%4The aqueous solution of F makees electrolyte, in oxidation voltage 10～60V bars of setting
Under part, aoxidize 30～180 minutes；Microcosmic nano tube structure can be formed on the surface of anode, what its electrode surface nanotube was formed
Principle is：1) in the presence of electric field, the water power near anode surface is from generation O2-, while titanium quickly dissolves, produce a large amount of Ti4 +, with O2-It is rapid to react, the oxidation titanium barrier layer of densification is formed in Ti polar board surfaces, it is main that following reaction occurs：
H2O→2H++O2- (1)
Ti-4e→Ti4+ (2)
Ti4++2O2-→TiO2 (3)
2) F in electrolyte solution-In the presence of electric field, migrate to anode, chemical action occurs with oxidation titanium barrier layer
Form the TiF of solubility6 2-, cause oxidation titanium barrier layer to form irregular indenture；With the prolongation of oxidization time, indenture by
Gradually develop pore-forming core, hole core becomes aperture because field makes peace chemical dissolution procedure again, and the density of aperture is continuously increased, it is last uniform
It is distributed in polar board surface and forms ordered structure, the reaction of main generation is：
TiO2+6F-+4H+→TiF6 2-+2H2O (4)
3) when aoxidizing titanium barrier layer and being equal with the dissolution velocity of bottom hole oxide layer to the speed that titanium substrate is advanced, the length in hole is not
It is further added by, ultimately forms independent orderly nano tube structure；
(5) the Ti pole plates with nanotube pattern for being formed are taken out after the completion of question response, after deionized water is cleaned by ultrasonic, then is done
It is dry to obtain finished product Ti nano-electrodes.
2. the method that a kind of Ti nano-electrodes according to claim 1 efficiently remove nitrate in groundwater, its feature exist
In：The cylindrically shaped or cubic cylindricality of the electrolysis bath described in step 3, between anode and negative electrode with macroion exchange membrane every
Open, make electrolysis bath become multiple-grooved form；Or macroion exchange membrane between anode and negative electrode, is not placed, make electrolysis bath become single cavity
Form.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083377A (en) * | 1996-02-22 | 2000-07-04 | Enpar Technologies Inc. | Electrochemical treatment of water contaminated with nitrogenous compounds |
| CN101857288A (en) * | 2010-06-18 | 2010-10-13 | 南京理工大学 | Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode |
| CN202576055U (en) * | 2012-05-21 | 2012-12-05 | 中国地质大学（北京） | Device for performing electrochemical reduction on nitrate |
| CN204022519U (en) * | 2014-08-25 | 2014-12-17 | 上海理工大学 | A kind of for the water treatment device except the nitric nitrogen that anhydrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3691461B2 (en) * | 2002-02-13 | 2005-09-07 | 三洋電機株式会社 | Water purification system and water purification method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083377A (en) * | 1996-02-22 | 2000-07-04 | Enpar Technologies Inc. | Electrochemical treatment of water contaminated with nitrogenous compounds |
| CN101857288A (en) * | 2010-06-18 | 2010-10-13 | 南京理工大学 | Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode |
| CN202576055U (en) * | 2012-05-21 | 2012-12-05 | 中国地质大学（北京） | Device for performing electrochemical reduction on nitrate |
| CN204022519U (en) * | 2014-08-25 | 2014-12-17 | 上海理工大学 | A kind of for the water treatment device except the nitric nitrogen that anhydrates |
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