CN105502584A - Device and method for removing ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater - Google Patents

Device and method for removing ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater Download PDF

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Publication number
CN105502584A
CN105502584A CN201510946566.8A CN201510946566A CN105502584A CN 105502584 A CN105502584 A CN 105502584A CN 201510946566 A CN201510946566 A CN 201510946566A CN 105502584 A CN105502584 A CN 105502584A
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China
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electrode
cod
nitrogen
anode
electrochemical reactor
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Chinese (zh)
Inventor
郭希山
郭迪
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to CN201510946566.8A priority Critical patent/CN105502584A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08Seawater, e.g. for desalination

Abstract

The invention discloses a device and method for removing ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater. A water inlet is formed in the top end of an impounding reservoir of the device and communicated with a water outlet in the upper end of an electrochemical reactor, and a water outlet is formed in the lower end of the impounding reservoir and connected with a water inlet in the lower end of the electrochemical reactor. An anode, a bipolar electrode and a cathode are sequentially arranged in the electrochemical reactor through a peristaltic pump, the anode is connected with a positive electrode of a direct-current stabilized power supply, and the cathode is connected with a negative electrode of the direct-current stabilized power supply. A chemical agent does not need to be added, and thus treatment cost can be greatly reduced; free chlorine is constantly generated in situ at the anode, and thus safety performance is improved; the treatment process is clean and quick, and sludge and secondary pollution are avoided; the ammonia nitrogen, nitrite nitrogen and COD removing speed is high, and efficiency is high; only the current size needs to be controlled, and thus control is easy; the device is simple and convenient to operate and maintain.

Description

The apparatus and method of ammonia nitrogen, nitrite nitrogen and COD are removed in marine culture wastewater
Technical field
The present invention relates to a kind of water treatment device and method, particularly relate to the apparatus and method removing ammonia nitrogen, nitrite nitrogen and COD in a kind of marine culture wastewater.
Background technology
Culture fishery is obtaining swift and violent development in recent years.The tremendous influence that the discharge of a large amount of breeding wastewater causes to surrounding enviroment, the deterioration of water environment, frequent occurrence, the eubiosis and species diversity are also destroyed.The deteriorating water quality of Cultivated water brings massive losses also to China's fishery economic.Ammonia nitrogen, nitrite nitrogen and COD are the principal pollutant in aquiculture waste water, are also several materials being difficult to most remove.The special technology for aquiculture waste water is also fewer at present, is mostly the method using for reference traditional wastewater place neck.For seawer system, the effect of salinity in seawater, and the difference of pollution structure and common Lu Yuan sewage in breeding wastewater, add the intractability of breeding wastewater.
Advanced treatment at present for ammonia nitrogen, nitrite nitrogen and COD can be divided into physics, chemistry and biological three classes.Wherein, physical treatment method mainly contains filtration-absorption method, ion exchange method, membrane technology, foam separating technology; Chemical treatment method mainly contains flocculating settling, oxidation sterilizing; Bioremediation mainly contains nitrated/denitrification, activated sludge process, biological filter etc.This several method has respective advantage when processing breeding wastewater, but also there is certain problem, as its effectiveness of biological process can not lasting stability, anti-poor environment impact capacity is poor, chemical method majority needs additionally to add chemical reagent, film process in Physical exists costly, produces the problems such as dense water and fouling membrane, and ion-exchange and absorption method face a difficult problem for adsorbent reactivation.Therefore, still need to find that a kind of technique is simple, treatment effect good, floor space is little, can the ammonia nitrogen of flexible operating, non-secondary pollution and low cost, nitrite nitrogen and COD treatment technology.
Summary of the invention
In order to solve Problems existing in background technology, a kind of electrochemistry is the object of the present invention is to provide to remove the apparatus and method of ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater.
In order to reach foregoing invention object, the technical solution used in the present invention is:
One, the device of ammonia nitrogen, nitrite nitrogen and COD is removed in a kind of marine culture wastewater
The present invention includes water reservoir, peristaltic pump, electrochemical reactor and D.C. regulated power supply; Water reservoir top is provided with water-in, and water-in is communicated with the water outlet of electrochemical reactor upper end, and water reservoir lower end is provided with water outlet, and water outlet is connected by the water-in of peristaltic pump with electrochemical reactor lower end; Electrochemical reactor is built with being equipped with anode, bipolar electrode and negative electrode successively, and anode is connected with the positive pole of D.C. regulated power supply, and negative electrode is connected with the negative pole of D.C. regulated power supply.
Described anode is platinum electrode, boron-doped diamond electrode, titanium titanizing plating ruthenium iridium electrode, titanium base plating iridium electrode or titanium base rhodanizing electrode; Described negative electrode is Graphite Electrodes, titanium plate, boron-doped diamond electrode, titanium titanizing plating ruthenium iridium electrode, titanium base plating iridium electrode or titanium base rhodanizing electrode; Described bipolar electrode is boron-doped diamond electrode or titanium titanizing plating ruthenium iridium electrode.
The anode of described electrochemical reactor, bipolar electrode and negative electrode are measure-alike circular flat plate electrode.
The anode of described electrochemical reactor inside and negative electrode are connected with the positive pole of D.C. regulated power supply and negative pole respectively, and bipolar electrode does not need to connect with wire.
Two, remove a method of ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater, the step of the method is as follows:
Step 1) enter water reservoir after the wastewater collection of discharging in marine culture wastewater;
Step 2) water outlet of water reservoir enters in the electrochemical reactor that anode, bipolar electrode and negative electrode are housed by peristaltic pump, start D.C. regulated power supply, water intake mode is from bottom in and top out, and the parallel of electrode places full and uniform the contacting ensureing electrode and the aqueous solution;
Step 3) in electrochemical reactor, Cl a large amount of in the aqueous solution -cl is oxidized at anode 2, the Cl of generation 2be dissolved in the aqueous solution and generate HOCl, wherein, HClO also ionizes and produces ClO -; Free chlorine comprises Cl 2, HOCl and OCl -, as strong oxidizer, mineralized nitrogen is become nitrogen, nitrite nitrogen changes into nitre nitrogen, and remove COD, namely complete electrochemical oxidation and remove ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater.
Step 1) described in marine culture wastewater, wherein, ammonia nitrogen concentration 0.1-10mg/L, nitrite nitrogen concentration 0.1-80mg/L, COD are 5-50mg/L.
Step 2) described in electrochemical reactor circular flow be 1L/min, current density is 0.5-10mA/cm 2, polar plate area is 10-100cm 2, polar plate spacing is 1-5cm, and hydraulic detention time is 10-40min.
Compared with traditional marine culture wastewater treatment process, as filtration-absorption method, ion exchange method, membrane technology, active sludge are compared with biological filter etc., the beneficial effect had of the present invention is:
(1) additional chemical agent is not needed, can significantly reduction processing cost;
(2) free chlorine (Cl2, HClO and ClO-) produces at anode continuous in situ, improves safety performance;
(3) treating processes is clean, quick, can not produce mud and secondary pollution;
(4) the removal speed of ammonia nitrogen, nitrite nitrogen and COD is fast, and efficiency is high;
(5) only need to control size of current, be easy to control;
(6) device is simple, convenient operation and maintenance.
Visible, the present invention is a kind of high efficiency technical of ammonia nitrogen, nitrite nitrogen and COD in process marine culture wastewater, has good development prospect.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Fig. 2 is the structure iron of the electrochemical reactor in the present invention.
Description of symbols in figure: 1, water reservoir; 2, peristaltic pump; 3, electrochemical reactor; 4, D.C. regulated power supply; 5, anode; 6, negative electrode; 7, bipolar electrode.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
As depicted in figs. 1 and 2, the present invention includes water reservoir 1, peristaltic pump 2, electrochemical reactor 3 and D.C. regulated power supply 4; Water reservoir 1 top is provided with water-in, and water-in is communicated with the water outlet of electrochemical reactor 3 upper end, and water reservoir 1 lower end is provided with water outlet, and water outlet is connected with the water-in of electrochemical reactor 3 lower end by peristaltic pump 2; Electrochemical reactor is built with being equipped with anode 5, bipolar electrode 7 and negative electrode 6 successively, and anode 5 is connected with the positive pole of D.C. regulated power supply 4, and negative electrode 6 is connected with the negative pole of D.C. regulated power supply 4.
Described anode 5 is platinum electrode, boron-doped diamond electrode, titanium titanizing plating ruthenium iridium electrode, titanium base plating iridium electrode or titanium base rhodanizing electrode; Described negative electrode 6 is Graphite Electrodes, titanium plate, boron-doped diamond electrode, titanium titanizing plating ruthenium iridium electrode, titanium base plating iridium electrode or titanium base rhodanizing electrode; Described bipolar electrode 7 is boron-doped diamond electrode or titanium titanizing plating ruthenium iridium electrode.
The anode 5 of described electrochemical reactor 3, bipolar electrode 7 and negative electrode 6 are measure-alike circular flat plate electrode.
The anode 5 of described electrochemical reactor 3 inside and negative electrode 6 are connected with the positive pole of D.C. regulated power supply 4 and negative pole respectively, and bipolar electrode 7 does not need to connect with wire.
Principle of the present invention is:
In DC electric field, the chlorion (Cl in water body -) at anode oxidized generation Cl 2, the Cl of generation 2be dissolved in water body and generate HClO, wherein, HClO also ionizes and produces ClO -, reaction equation is as follows:
2Cl -→Cl 2+2e -
Cl 2+H 2O→HOCl+H ++Cl -
HOCl→H ++OCl -
Because free chlorine (comprises Cl 2, HOCl and OCl -) be strong oxidizer, so ammonia nitrogen, nitrite nitrogen and COD in water body can be removed by Quick Oxidation.
Staying water described in each embodiment, is and takes from marine park, Mouping, Yantai, Shandong.In each embodiment, the starting point concentration of ammonia nitrogen, nitrite nitrogen and COD controls respectively within the scope of 0.1-10mg/L, 0.1-80mg/L and 5-50mg/L, covers the concentration range of ammonia nitrogen, nitrite nitrogen and COD in general marine park.
Embodiment 1
Shown in composition graphs 1 and Fig. 2, the method that electrochemistry removes ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater is carried out according to the following steps:
Water reservoir 1 is entered after the wastewater collection of, discharging in marine culture wastewater;
Two, the water outlet of water reservoir 1 enters in the electrochemical reactor 3 that anode 5, bipolar electrode 7 and negative electrode 6 are housed by peristaltic pump 2, start D.C. regulated power supply 4, water intake mode is from bottom in and top out, and the parallel placement of electrode can ensure full and uniform the contacting of electrode and the aqueous solution;
Three, in electrochemical reactor 3, Cl a large amount of in the aqueous solution -cl is oxidized at anode 2, the Cl of generation 2be dissolved in the aqueous solution and generate HOCl, wherein, HClO also ionizes and produces ClO -.Free chlorine (comprises Cl 2, HOCl and OCl -) as strong oxidizer, mineralized nitrogen is become nitrogen, nitrite nitrogen changes into nitre nitrogen,
And remove COD, namely complete electrochemical oxidation and remove ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater.
Described anode, negative electrode and bipolar electrode are area 60cm 2boron-doped diamond electrode (purchased from NeoCoat company of Switzerland), polar plate spacing is 1cm.
In described electrochemical reactor 3, circular flow is 1L/min, and hydraulic detention time is 25min, and current density is 8mA/cm 2.
After testing, before and after process, the concentration of ammonia nitrogen, nitrite nitrogen and COD is as shown in table 1.
Table 1: the concentration (mg/L) processing forward and backward typical ammonia nitrogen, nitrite nitrogen and COD
Embodiment 2
Treatment process is compared with embodiment 1, and difference is only: current density is 4mA/cm 2.
After testing, before and after process, the concentration of ammonia nitrogen, nitrite nitrogen and COD is as shown in table 2.
Table 2: the concentration (mg/L) processing forward and backward typical ammonia nitrogen, nitrite nitrogen and COD
Embodiment 3
Treatment process is compared with embodiment 1, and difference is only: ammonia nitrogen, nitrite nitrogen are different with the starting point concentration of COD.
After testing, before and after process, the concentration of ammonia nitrogen, nitrite nitrogen and COD is as shown in table 3.
Table 3: the concentration (mg/L) processing forward and backward typical ammonia nitrogen, nitrite nitrogen and COD
Embodiment 4
Treatment process is compared with embodiment 1, difference is only: the anode that the present embodiment adopts is titanium plating ruthenium iridium electrode (purchased from Bo Rui Industrial materials Science and Technology Ltd. of Suzhou City), and negative electrode is titanium plate (purchased from Bo Rui Industrial materials Science and Technology Ltd. of Suzhou City).
After testing, before and after process, the concentration of ammonia nitrogen, nitrite nitrogen and COD is as shown in table 4.
Table 4: the concentration (mg/L) processing forward and backward typical ammonia nitrogen, nitrite nitrogen and COD
Embodiment 5
Treatment process is compared with embodiment 4, and difference is only: current density is 4mA/cm 2.
After testing, before and after process, the concentration of ammonia nitrogen, nitrite nitrogen and COD is as shown in table 5.
Table 5: the concentration (mg/L) processing forward and backward typical ammonia nitrogen, nitrite nitrogen and COD
Embodiment 6
Treatment process is compared with embodiment 4, and difference is only: ammonia nitrogen, nitrite nitrogen are different with the starting point concentration of COD.
After testing, before and after process, the concentration of ammonia nitrogen, nitrite nitrogen and COD is as shown in table 6.
Table 6: the concentration (mg/L) processing forward and backward typical ammonia nitrogen, nitrite nitrogen and COD
Above-mentioned embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment made the present invention is equivalent replaces and improvement etc., all falls into protection scope of the present invention.

Claims (7)

1. remove a device of ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater, it is characterized in that: comprise water reservoir (1), peristaltic pump (2), electrochemical reactor (3) and D.C. regulated power supply (4); Water reservoir (1) top is provided with water-in, and water-in is communicated with the water outlet of electrochemical reactor (3) upper end, and water reservoir (1) lower end is provided with water outlet, and water outlet is connected with the water-in of electrochemical reactor (3) lower end by peristaltic pump (2); Electrochemical reactor is built with being equipped with anode (5), bipolar electrode (7) and negative electrode (6) successively, and anode (5) is connected with the positive pole of D.C. regulated power supply (4), and negative electrode (6) is connected with the negative pole of D.C. regulated power supply (4).
2. remove the device of ammonia nitrogen, nitrite nitrogen and COD in a kind of marine culture wastewater according to claim 1, it is characterized in that: described anode (5) is platinum electrode, boron-doped diamond electrode, titanium titanizing plating ruthenium iridium electrode, titanium base plating iridium electrode or titanium base rhodanizing electrode; Described negative electrode (6) is Graphite Electrodes, titanium plate, boron-doped diamond electrode, titanium titanizing plating ruthenium iridium electrode, titanium base plating iridium electrode or titanium base rhodanizing electrode; Described bipolar electrode (7) is boron-doped diamond electrode or titanium titanizing plating ruthenium iridium electrode.
3. remove the device of ammonia nitrogen, nitrite nitrogen and COD in a kind of marine culture wastewater according to claim 1, it is characterized in that: the anode (5) of described electrochemical reactor (3), bipolar electrode (7) and negative electrode (6) are measure-alike circular flat plate electrode.
4. in a kind of marine culture wastewater according to claim 1, remove the device of ammonia nitrogen, nitrite nitrogen and COD, it is characterized in that: the inner anode (5) of described electrochemical reactor (3) and negative electrode (6) are connected with the positive pole of D.C. regulated power supply (4) and negative pole respectively, and bipolar electrode (7) does not need to connect with wire.
5., for removing the method for ammonia nitrogen, nitrite nitrogen and COD in a kind of marine culture wastewater according to claim 1, it is characterized in that, the step of the method is as follows:
Step 1) enter water reservoir (1) after the wastewater collection of discharging in marine culture wastewater;
Step 2) water outlet of water reservoir (1) enters in the electrochemical reactor (3) that anode (5), bipolar electrode (7) and negative electrode (6) are housed by peristaltic pump (2), start D.C. regulated power supply (4), water intake mode is from bottom in and top out, and the parallel of electrode places full and uniform the contacting ensureing electrode and the aqueous solution;
Step 3) inner at electrochemical reactor (3), Cl a large amount of in the aqueous solution -cl is oxidized at anode 2, the Cl of generation 2be dissolved in the aqueous solution and generate HOCl, wherein, HClO also ionizes and produces ClO -; Free chlorine comprises Cl 2, HOCl and OCl -, as strong oxidizer, mineralized nitrogen is become nitrogen, nitrite nitrogen changes into nitre nitrogen, and remove COD, namely complete electrochemical oxidation and remove ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater.
6. in a kind of marine culture wastewater according to claim 5, remove the method for ammonia nitrogen, nitrite nitrogen and COD, it is characterized in that: step 1) described in marine culture wastewater, wherein, ammonia nitrogen concentration 0.1-10mg/L, nitrite nitrogen concentration 0.1-80mg/L, COD are 5-50mg/L.
7. remove the method for ammonia nitrogen, nitrite nitrogen and COD in a kind of marine culture wastewater according to claim 5, it is characterized in that: step 2) described in electrochemical reactor (3) circular flow be 1L/min, current density is 0.5-10mA/cm 2, polar plate area is 10-100cm 2, polar plate spacing is 1-5cm, and hydraulic detention time is 10-40min.
CN201510946566.8A 2015-12-17 2015-12-17 Device and method for removing ammonia nitrogen, nitrite nitrogen and COD in marine culture wastewater Pending CN105502584A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110038647A (en) * 2019-05-13 2019-07-23 南京大学 A kind of method of electrolysed saline solution highly efficient regeneration resin

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CN1499925A (en) * 2001-04-16 2004-05-26 松鼠技术私人有限公司 Method of shrimp farming in seawater or brackish water ponds
CN1898162A (en) * 2003-12-18 2007-01-17 阿克佐诺贝尔公司 Electrolytic cell for treating contaminated water
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CN103361670A (en) * 2008-09-30 2013-10-23 德诺拉工业有限公司 Cathode member and bipolar plate for hypochlorite cells
CN105130070A (en) * 2015-09-05 2015-12-09 浙江大学 Device and method for removing ammonia nitrogen in output water of seawater denitrification reactor
CN205241294U (en) * 2015-12-17 2016-05-18 浙江大学 Get rid of ammonia nitrogen, inferior nitre nitrogen and COD's device in mariculture waste water

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002010724A (en) * 2000-06-29 2002-01-15 Babcock Hitachi Kk Method for decomposing ammonia in sea water and device therefor
CN1499925A (en) * 2001-04-16 2004-05-26 松鼠技术私人有限公司 Method of shrimp farming in seawater or brackish water ponds
CN1898162A (en) * 2003-12-18 2007-01-17 阿克佐诺贝尔公司 Electrolytic cell for treating contaminated water
CN103361670A (en) * 2008-09-30 2013-10-23 德诺拉工业有限公司 Cathode member and bipolar plate for hypochlorite cells
CN103201412A (en) * 2010-11-22 2013-07-10 三菱重工环境·化学工程株式会社 Seawater electrolysis system and seawater electrolysis method
CN105130070A (en) * 2015-09-05 2015-12-09 浙江大学 Device and method for removing ammonia nitrogen in output water of seawater denitrification reactor
CN205241294U (en) * 2015-12-17 2016-05-18 浙江大学 Get rid of ammonia nitrogen, inferior nitre nitrogen and COD's device in mariculture waste water

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110038647A (en) * 2019-05-13 2019-07-23 南京大学 A kind of method of electrolysed saline solution highly efficient regeneration resin
CN110038647B (en) * 2019-05-13 2021-06-11 南京大学 Method for efficiently regenerating resin by using electrolytic salt solution

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