CN204644026U - A kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water - Google Patents
A kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water Download PDFInfo
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- CN204644026U CN204644026U CN201520093314.0U CN201520093314U CN204644026U CN 204644026 U CN204644026 U CN 204644026U CN 201520093314 U CN201520093314 U CN 201520093314U CN 204644026 U CN204644026 U CN 204644026U
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Abstract
A kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water, comprise sewage surge tank, electrolysis/dual wavelength ultraviolet line irradiated in situ case and HClO, clorox and ozone decomposed case, the outlet of the bottom of sewage surge tank is connected with the water-in bottom electrolysis/dual wavelength ultraviolet line irradiated in situ case by sump pump, and the water outlet of electrolysis/dual wavelength ultraviolet line irradiated in situ upper box part is connected with the water-in of HClO, clorox and ozone decomposed lower box part; Aeration tube and agitator is provided with in sewage surge tank; At electrolysis/dual wavelength ultraviolet line irradiated in situ case built with electrolysis electrode, dual wavelength ultraviolet line lamp is set in the side, gap of electrolysis electrode; At HClO, clorox and ozone decomposed case built with Single wavelength ultraviolet lamp.The utility model can overcome physico-chemical process and rise the deficiency of biochemical process existence, simultaneously compared with other electrochemical processes, has the treatment time short, ammonia nitrogen removal frank high.Ammonia nitrogen removal frank reaches more than 90%.
Description
Technical field
The utility model relates to the sewage disposal technology of field of environment engineering, specifically a kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water.
Background technology
Along with developing rapidly and the continuous expansion of city size of global industry, the pollution of pollutent to water body environment of living and emit in production process is on the rise, wherein one of the nitrogenous compound of different sources important pollutent having become water body environment.Ammonia nitrogen in water is mainly derived from the decomposition of itrogenous organic substance in sanitary sewage, the trade effluent such as coking, synthetic ammonia, farmland drainage and nature process etc.According to statistics, what be in eutrophic state in China's Main Lakes because of nitrogen and phosphorus pollution accounts for 56% more than of statistics lake total amount.A large amount of nitrogen compounds enters water body environment, causes Water quality to worsen, and affects fishery, agricultural and town environment quality, and then affects HUMAN HEALTH.In sewage, nitrogen exists with ammonia nitrogen, organonitrogen, nitrite nitrogen and nitrate nitrogen four kinds of forms.Ammonia nitrogen in sewage is the product of microbial activities, the size of ammonia nitrogen amount in water, is the index weighing degree of water pollution.
Traditional sewage water denitrification technology is summed up and can be divided into physico-chemical process and biological process, is described below respectively.
(1) physico-chemical process sewage water denitrification technology, comprising:
A. blow-off method: blow-off method is mainly used in the removal of ammonia nitrogen in waste water.Its principle passes in water by air or other carrier gas, gas fully contacted with waste water, thus makes the NH in waste water
3to gas phase transfer, reach the object removing ammonia nitrogen in water.In the basic conditions, free ammonia nitrogen is become to be blown, to remove the method for NH3-N in waste water also referred to as ammonia still process method mineralized nitrogen in waste water by steam air lift.
The method is suitable for processing high-concentration ammonia nitrogenous wastewater, except ammonia effect stability, simple to operate, but easily causes secondary pollution, and as adopted ammonia to steam method in the basic conditions, then need to consume a large amount of alkali, production cost is high.
B. absorption method: the ammonia nitrogen in system is adsorbed on adsorbent surface by the specific surface area utilizing sorbent material larger and adsorptive power or ion-exchange capacity firmly, by desorption and the regeneration of sorbent material, removes the nitrogen-containing pollutant in water or recycles.Conventional sorbent material has gac, natural mineral, haydite, ion exchange resin etc.
The method environmental protection, material source is wide, and technique is simple.But materials adsorption finite capacity, regeneration is frequent, and regenerating unit is complicated, and the adsorbent capacity after regeneration declines.
C. Wet Catalytic Oxidation Method: catalytic wet air oxidation is under certain temperature, pressure, under the effect of catalyzer, is that oxygenant makes the itrogenous organic substance in sewage resolve into N with air or oxygen
2, thus reach the object of denitrogenation.
The method speed of response is fast, and floor space is little, non-secondary pollution, and processing efficiency is high.But need heat up pressurization, and processing cost is high, require strict to reaction conditions, equipment etc., catalyzer is expensive.
D. break point chlorination method: the chlorine of q.s or clorox are put in waste water, reach certain some time, free chlorine contents contained in waste water is lower, and ammonia-nitrogen content trends towards zero; Free chlorine contents when chlorine intake exceedes this in water rises, and this point is often called break, and chlorination is in this case called breakpoint chlorination, and the ammonia nitrogen in waste water is oxidized to nitrogen and is divested.Concrete reaction process is as follows:
（1）
（2）
（3）
（4）
The method speed of response is fast, needs equipment few, but the safe handling of liquid chlorine and storage request high, processing cost is also higher.If replace liquid chlorine with clorox or chlorine dioxide generating device, although safer, working cost can decline to some extent, and device is expensive.
E. chemical precipitation method: chemical precipitation method mainly by adding certain chemical agent in waste water, make it to react with the nitrogenous organic or inorganic thing in waste water, form difficulty soluble salt and precipitate, thus reduce the method for nitrogen content in water.At present, most study is add containing Mg in waste water
2+and PO4
3-medicament.Concrete reaction process is as follows:
（5）
（6）
（7）
The method speed of response is fast, simple to operate, can Automated condtrol.But the large usage quantity of precipitation agent, need adjust the pH of sewage.The mud produced is difficult.
F. catalytic reduction: namely catalytic reduction take hydrogen as reductive agent, under metal catalyst effect, nitrate nitrogen is reduced into the process of the nitrogen of environmental sound.Because of its have speed of response soon, do not change tap water ultimate constituent, do not produce secondary pollution and the simple advantage of reaction unit structure and be considered to one of the most promising denitride technology.
The method cleans non-secondary pollution, and speed of response is fast, can adapt to differential responses condition, be easy to operational management.But the activity and selectivity of catalyzer is wayward.
G. membrane separation process: membrane separation process be utilize the film with selective penetrated property that is natural or synthetic, with outside energy or chemical potential difference for impellent realizes the process of various Component seperation, the membrane separation process for denitrogenation of waste water comprises reverse osmosis and electrodialysis two kinds.Separatory film has selective permeability, conventional reverse osmosis membrane mainly acetate membrane.
The method processing efficiency is high, and without phase transformation, modularization, flow process is simple, power consumption is low.But easily occur fouling membrane, poor stability, running cost are high, can only process low concentration wastewater, and complicated components waste water needs pre-treatment.
(2) biological process denitride technology:
The main bio-denitrifying sewage technology adopted realizes time or aerobic, anaerobic environment spatially by reactor and control device at present, reaches the object of nitration denitrification denitrogenation.Nitrification is namely little at aerobic condition, and ammonium oxidation is nitrous acid (salt) and nitric acid (salt) by autotrophic type nitrobacteria; Denitrification refers to that nitrous acid (salt) and nitric acid (salt) are reduced to the process of nitrogen by different oxygen type denitrifying bacteria under anoxic or anaerobic condition.At present, the method that bio-denitrifying sewage is the most general combines nitration reaction and anti-nitration reaction two processes exactly.The first step comprises two kinds of effects, first be nitrite by Nitrite bacteria by ammonia oxidation, and then be nitrate by nitrobacteria by nitrite-oxidizing, second step is the acting in conjunction having kind of microorganism, take organism as electron donor, be first nitrite by nitrate reduction and then be reduced to nitrogen and discharge, reach the object of denitrogenation.Active sludge denitrification process and biomembrane denitrogenation technique is divided into according to the difference of sewage treatment process.The concrete denitrification reaction of biological process is as follows:
（8）
（9）
Total reaction:
（10）
Anti-nitration reaction refers under anaerobic, and nitrate nitrogen and nitrite nitrogen are reduced to the process of nitrogen by denitrifying bacteria, and its reaction is as follows:
（11）
（12）
Total reaction:
(13)
Biological process is environmentally friendly, high performance cheap, reduces secondary pollution.But traditional bio-denitrification technology is main, and also there are the following problems: nitrobacteria is autotrophic bacteria, poor growth; It is very responsive that nitrobacteria impacts especially toxic impact to water quality and quantity, and effluent quality easily fluctuates; Nitrification and denitrification process is difficult to unify over time and space, and nitric efficiency is low; Some trade effluents just must can carry out biological denitrificaion by additional carbon.
Current electrochemical process denitrogenation is just becoming the focus of denitrogenation research, adopt the electrochemical oxidation process that titanium ruthenium iridium is anode, stainless steel is negative electrode to process refuse leachate if any investigator, utilize SPR anode electrolysis treating refuse penetrating fluid, adopt electrochemical oxidation process treatment of simulated high-concentration ammonia nitrogenous wastewater; Treatment time from 2 hours to 7 hours not etc., NH
4+ionic concn clearance be 53.6% or nitrogen removal rate reach 87.35%.Ammonia nitrogen solution after above electrochemical process process, process product is N
2, NO
2 -or NO
3 -, generate NO
2 -or NO
3 -after, also need to carry out anti-nitration reaction further and change N into make final reacting product
2thus total nitrogen concentration in reduction water.
Remove the process of ammonia nitrogen and total nitrogen from existing electrochemistry, total process of denitrogenating generally needs some hours, and the treatment time is still longer, and can be NO by mineralized nitrogen in some cases
2 -or NO
3 -, also need to carry out anti-nitration reaction to reduce total nitrogen content further combined with other technologies, technique is comparatively complicated.
summary of the invention
The utility model provides a kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water, to solve secondary pollution, adsorbent reactivation difficulty that existing physico-chemical process exists, catalyzer is expensive, active and selectivity is wayward, cost is high, produce unmanageable mud and easily occur fouling membrane and biological process bacterial growth slow, anti-water quality and quantity impact poor, go out the treatment time needed for water unstable and existing electrochemical process longer, easy by mineralized nitrogen for NO
2 -or NO
3 -etc. technical problem.
The technical solution of the utility model is: a kind of device adopting PhotoelectrochemicalTechnique Technique to remove the method for ammonia nitrogen in water, it is characterized in that, comprise sewage surge tank, electrolysis/dual wavelength ultraviolet line irradiated in situ case and HClO, clorox and ozone decomposed case, the outlet of the bottom of sewage surge tank is connected with the water-in bottom electrolysis/dual wavelength ultraviolet line irradiated in situ case by sump pump, the water outlet of electrolysis/dual wavelength ultraviolet line irradiated in situ upper box part and HClO, the water-in of clorox and ozone decomposed lower box part connects, sewage after process flows out from the water outlet being located at this HClO and ozone decomposed upper box part, aeration tube and agitator is provided with in described sewage surge tank, at this electrolysis/dual wavelength ultraviolet line irradiated in situ case built with electrolysis electrode, dual wavelength ultraviolet line lamp is vertically set in the side, negative electrode and positive electrode gap of electrolysis electrode, at described HClO, clorox and ozone decomposed case built with Single wavelength ultraviolet lamp.
Described dual wavelength ultraviolet line lamp can send the dual wavelength ultraviolet line of 254nm and 185nm wavelength; Described Single wavelength ultraviolet lamp can send the Single wavelength ultraviolet that wavelength is 254nm.
Described dual wavelength ultraviolet line lamp and Single wavelength ultraviolet lamp all seal and are arranged in quartz lamp cover.
Technique effect of the present utility model is: the sewage that electrolysis contains certain salinity produces hypochlorous acid (or clorox), dual wavelength ultraviolet line (185nm+254nm) irradiated in situ, Single wavelength ultraviolet (254nm) irradiate and be oxidized further and take out the PhotoelectrochemicalMethod Method of residual ozone, utilizes the principal reaction oxidizing substance such as HClO, clorox, O3, OH and [O] to be N by mineralized nitrogen in water
2, thus reduce ammonia nitrogen and total nitrogen content in water.Physico-chemical process can be overcome and rise the deficiency that biochemical process exists, simultaneously compared with other electrochemical processes, there is the treatment time short, ammonia nitrogen removal frank high.Ammonia nitrogen waste water after method and system process described in the utility model, ammonia nitrogen removal frank reaches more than 90%.
Accompanying drawing explanation
Fig. 1 is the device formation schematic diagram that the utility model PhotoelectrochemicalTechnique Technique removes ammonia nitrogen in water.
Description of reference numerals: 1. sewage surge tank; 2. electrolysis/dual wavelength ultraviolet line irradiated in situ case; 3. HClO, clorox and ozone decomposed case; 4. sump pump; 5. aeration tube; 6. agitator; 7. quartz lamp cover; 8. double-wavelength ultraviolet lamp; 9. electrolysis electrode; 10. Single wavelength ultraviolet lamp.
Embodiment
See Fig. 1, a kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water of the utility model, comprising:
(1) sewage surge tank 1: for regulating the salinity dissolved oxygen concentration of processed sewage, by sewage from and the mouth of a river be filled with sewage surge tank 1, be transported to follow-up treatment unit from water outlet after adjustment.The outlet of the bottom of sewage surge tank 1 is connected with the water-in bottom electrolysis/dual wavelength ultraviolet line irradiated in situ case 2 by sump pump 4.Aeration tube 5 and agitator 6 is provided with in sewage surge tank 1.
(2) electrolysis/dual wavelength ultraviolet line irradiated in situ case 2: irradiate sewage for electrolyzing sewage with dual wavelength ultraviolet line, overlapping built with electrolysis electrode 9(negative electrode and anode transpostion interval at the casing of this electrolysis/dual wavelength ultraviolet line irradiated in situ case 2), a double-wavelength ultraviolet lamp 8 is set at the left side vertical of negative electrode and anode, shines to the right from the gap between negative electrode and positive electrode during work.Double-wavelength ultraviolet lamp 8 can send the dual wavelength ultraviolet line (on sale on market) of 254nm and 185nm wavelength.The photon energy of the UV-lamp of 185nm wavelength is comparatively large, has comparatively high de-agglomeration ability, and its ionizing event can utilize ambient air to produce ozone, and ozone is decomposed into atomic oxygen and oxygen under ultraviolet 254nm, and its induced by atomic oxygen is as lively as a cricket; And 254nm UV photons can ozone decomposition, ensure that ozone is not overflowed, in order to avoid harm health simultaneously.
Electrolytic current density scope in described electrolysis/dual wavelength ultraviolet line irradiated in situ case 2 is 20-100mA/cm
2, the sewage residual chlorine concentration in its exit is 2-10mg/L.The water-in of the water outlet on electrolysis/dual wavelength ultraviolet line irradiated in situ case 2 top and HClO, clorox and ozone decomposed case 3 bottom is connected.
(3) HClO, clorox and ozone decomposed case 3: for decomposing the sewage flowed out from described electrolysis/dual wavelength ultraviolet line irradiated in situ case 2, be the Single wavelength ultraviolet lamp 10 of 254nm at this HClO, clorox and ozone decomposed case 3 built with wavelength, the sewage flow through is irradiated.
Described dual wavelength ultraviolet line lamp 8 and Single wavelength ultraviolet lamp 10 all seal and are arranged in quartz lamp cover 7.
Use treating processes of the present utility model as follows:
1, regulating water body to being applicable to salinity, regulating oxygen in water to being applicable to concentration:
Electrolyzing sewage needs suitable salinity.Before sewage enters reaction unit, first measure water salinity, if salinity is lower than 3PSU, then adding NaCl(also can be the not virose soluble chloride of tool such as KCl or MgCl), water salinity is not less than 3PSU; If water salinity is not less than 3PSU, then without the need to adding ionogen.Salinity Wei≤3PSU needed for electrolysis in the utility model.
Measuring and while regulating salinity, measuring content of oxygen dissolved in water, if content of oxygen dissolved in water is lower than 2mg/l, then to water body air-blowing, regulate oxygen in water Han Liang≤5mg/l.Required inflow water dissolution oxygen level Ying≤5mg/l in the utility model.
2, electrolyzing sewage+dual wavelength ultraviolet line irradiated in situ electrode reaction region water body:
After the sewage with certain salinity enters electrolysis/ultraviolet lighting case by sewage surge tank, during electrode pad region, electrode starts electrolysis, and negative electrode, anode generation electrochemical reaction produce clorox, and concrete reaction is as follows:
Anode:
(14)
Negative electrode:
(15)
The Cl that anode generates
2rapid water-soluble generation hypochlorous acid or clorox:
(16)
（17）
HClO or NaClO generated has oxidisability, can be oxidized ammonia nitrogen.React as follows:
（18）
In the utility model, electrolytic current density scope is 20-100mA/cm
2, electrolysis/dual wavelength ultraviolet illumination reaction case exit residual chlorine concentration is 2-10mg/L.
In addition, while electrolysis produces HClO and NaClO, also OH can be produced at the electrode surface, equally ammonia nitrogen in meeting oxidizing water.Concrete reaction is as follows:
（19）
While electrolysis produces HClO and OH, utilize dual wavelength ultraviolet line irradiation electrode conversion zone.Dual wavelength ultraviolet line lamp can send the UV-lamp of 254nm and 185nm wavelength simultaneously when referring to work.The UV-lamp of 185nm wavelength, photon energy is comparatively large, and the ultraviolet ionizing event of 185nm can utilize the dissolved oxygen in water body to produce ozone, and concrete reaction is as follows:
（20）
（21）
（22）
In formula:
hvfor ultraviolet photon, M is that the molecule of wall of container and electrode does catalytic substance, produces ozone.
Be radiated at through 185nm length ultraviolet the ozone produced in water and have oxidisability, oxidable mineralized nitrogen is N
2.0.5-3mg/l is should be at electrolysis/dual wavelength ultraviolet illumination reaction case exit ozone concn.
While 185nm length ultraviolet irradiates, the ultraviolet of 254nm wavelength also irradiates electrolytic reaction region simultaneously, under 254nm length ultraviolet irradiates, occurs to react as follows:
（23）
（24）
Under 254nm ultraviolet irradiation, newly-generated HClO and O
3while oxidation ammonia nitrogen, decomposite again the oxygen of atomic state, this atomic oxygen has extremely strong oxidisability, can be N by ammonium oxidation
2.
A UV-lamp is vertically positioned at side, cathode and anode gap, shines to opposite side during work from side, gap.Be 200uW/cm in the corresponding lateral edges uv irradiation strength range of ultraviolet lamp in the utility model
2-1900 uW/cm
2.
The time that sewage flows through to exit from electrolysis/dual wavelength ultraviolet illumination reaction tank inlet is 20 seconds-120 seconds, and the reaction times of sewage in reaction box is 20 seconds-120 seconds.
In electrolysis/dual wavelength ultraviolet illumination reaction case, the ammonia nitrogen of sewage is under the effect of the principal reaction oxidizing substance such as HClO, NaClO, O3, OH and [O], by regulating the reaction parameter such as current density, HClO, NaClO generation concentration, intensity of illumination, reaction times, ammonia nitrogen in sewage is made to be oxidized to N efficiently, selectively at short notice
2, and can not NO be further oxidized to
2 -or NO
3 -.
3, sewage flows into HClO, clorox and ozone decomposed case after electrolysis/dual wavelength ultraviolet illumination reaction case process
Sewage after electrolysis/dual wavelength ultraviolet illumination reaction case process flows into HClO and ozone decomposed case.Due in now sewage still containing the chlorine residue of 2-10mg/L and the ozone of 0.5-3mg/l, then can cause secondary pollution if do not added process discharge.In HClO, NaClO and ozone decomposed case, install Single wavelength (254nm) ultraviolet lamp and irradiate, HClO, clorox and ozone are decomposed.Finally from the water body that HClO, NaClO and the outlet of ozone decomposed case flow out, HClO, NaClO and ozone concn are all less than 0.1mg/l, thus reach green discharge.
Claims (3)
1. the device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water, it is characterized in that, comprise sewage surge tank, electrolysis/dual wavelength ultraviolet line irradiated in situ case and HClO, clorox and ozone decomposed case, the outlet of the bottom of sewage surge tank is connected with the water-in bottom electrolysis/dual wavelength ultraviolet line irradiated in situ case by sump pump, the water outlet of electrolysis/dual wavelength ultraviolet line irradiated in situ upper box part is connected with the water-in of HClO, clorox and ozone decomposed lower box part, and the sewage after process flows out from the water outlet being located at this HClO and ozone decomposed upper box part; Aeration tube and agitator is provided with in described sewage surge tank; At this electrolysis/dual wavelength ultraviolet line irradiated in situ case built with electrolysis electrode, dual wavelength ultraviolet line lamp is vertically set in the side, negative electrode and positive electrode gap of electrolysis electrode; At described HClO, clorox and ozone decomposed case built with Single wavelength ultraviolet lamp.
2. employing PhotoelectrochemicalTechnique Technique according to claim 1 removes the device of ammonia nitrogen in water, and it is characterized in that, described dual wavelength ultraviolet line lamp can send the dual wavelength ultraviolet line of 254nm and 185nm wavelength; Described Single wavelength ultraviolet lamp can send the Single wavelength ultraviolet that wavelength is 254nm.
3. employing PhotoelectrochemicalTechnique Technique according to claim 1 removes the device of ammonia nitrogen in water, it is characterized in that, described dual wavelength ultraviolet line lamp and Single wavelength ultraviolet lamp all seal and be arranged in quartz lamp cover.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891717A (en) * | 2015-02-10 | 2015-09-09 | 青岛双瑞海洋环境工程股份有限公司 | Method and apparatus for removing ammonia nitrogen in water by utilizing photoelectrochemical technology |
| CN111233224A (en) * | 2019-12-30 | 2020-06-05 | 南开大学 | Treatment method for simultaneously removing nitrogen, phosphorus and antibiotics in mariculture wastewater and sterilizing |
| CN112744893A (en) * | 2021-01-28 | 2021-05-04 | 清华大学 | Device and method for treating bacteriostatic agent in water by adopting persulfate |
-
2015
- 2015-02-10 CN CN201520093314.0U patent/CN204644026U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891717A (en) * | 2015-02-10 | 2015-09-09 | 青岛双瑞海洋环境工程股份有限公司 | Method and apparatus for removing ammonia nitrogen in water by utilizing photoelectrochemical technology |
| CN111233224A (en) * | 2019-12-30 | 2020-06-05 | 南开大学 | Treatment method for simultaneously removing nitrogen, phosphorus and antibiotics in mariculture wastewater and sterilizing |
| CN112744893A (en) * | 2021-01-28 | 2021-05-04 | 清华大学 | Device and method for treating bacteriostatic agent in water by adopting persulfate |
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