CN102086077B - Pulse electrochemical process for removing ammonia-nitrogen in landfill leachate - Google Patents
Pulse electrochemical process for removing ammonia-nitrogen in landfill leachate Download PDFInfo
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Abstract
The invention relates to a variable-frequency pulse electrochemical process for removing ammonia-nitrogen in landfill leachate. Variable-frequency pulse electrochemical pretreatment is carried out before anaerobic biological treatment and aerobic biological treatment or variable-frequency pulse electrochemical deep treatment is carried out after the anaerobic biological treatment and the aerobic biological treatment; the variable-frequency pulse electrochemical treatment adopts a variable-frequency pulse electrochemical device which comprises an electrobath and a variable-frequency pulse power supply connected with an electrode plate of the electrobath, wherein the variable-frequency pulse power supply is arranged in a power cabinet, the input end of the variable-frequency pulse power supply is externally connected with a three-phase power of 380V/50Hz, the output ends are used for guiding out anode and cathode which are respectively connected with the positive pole and the negative pole of the electrode plate of the electrobath, and a control panel of the power cabinet is provided with frequency, voltage and current adjusting buttons. Due to the adoption of the variable-frequency pulse electrochemical process, the ammonia-nitrogen removal rate can reach 70-100 percent, and the effluent of the landfill leachate with the unit electricity consumption of 4-8 kwh/m<3>, which is treated by the full process line, has the NH3-N content less than 6 mg/L and reaches the emission standard of national municipal solid waste landfill pollution control standard of GB16889-2008.
Description
Technical field
The present invention relates to water and pollute processing technology field, be specifically related to a kind of variable-frequency pulse electrochemical process of removing ammonia-nitrogen in percolate.
Background technology
Landfill method is the main method of present stage China's garbage treatment.After organic waste in domestic refuse enters landfill yard, carry out materialization and bio-degradation reactions, add rainwater, surface water and Groundwater infiltration landfill yard, just produced a kind ofly contain high concentration suspended matter, high density is organic and the liquid of inorganic components, i.e. percolate.
The foreign scholar has carried out a large amount of explorations and research with regard to the processing of percolate in recent ten years, has obtained some successful experiences, and what have is used for engineering practice.China is obtaining the experience of lot of valuable aspect the processing research of percolate.But the property complicated and changeable due to the percolate water quality and quantity, there is no at present very perfect treatment process, particular case and economic technology thereof according to different landfill yards requires to take respectively treatment process targetedly mostly, and these existing treatment process are difficult to reach the discharging standards of percolate mostly.Its subject matter has two:
The one, percolate high strength ammonia-nitrogen problem: garbage filter liquefied ammonia-nitrogen concentration also has the minority percolate to contain ammonia-nitrogen more than 5000mg/L generally at 200-5000mg/L.Because the ammonia-nitrogen of high density has certain restraining effect to biological treatment system, the ammonia-nitrogen of high density causes the C/N in percolate out of proportion simultaneously, and biological denitrificaion is difficult to carry out, and causes final outflow water ammonia-nitrogen index to be difficult to up to standard.
The 2nd, the problem that the percolate biodegradability is poor: in general, the CODcr in percolate has 500～600mg/L to process with biotechnology nearly.
China's urban domestic refuse sanitation burying landfill and percolate thereof are processed and are started late, and are mainly originally take ammonia stripping+anaerobism+aerobic as main.
After 2000, due to the develop rapidly of economy, newly-built Refuse Leachate Treatment Plant is generally away from the city, and percolate does not have condition to enter municipal sewage pipe network, therefore also corresponding raising of emission standard, discharging must reach GB16889-2008 " household refuse landfill sites pollution control criterion ".If the percolate of this moment only depends on biological treatment, its ammonia-nitrogen index can't reach emission request.
Percolate is a kind of composition complex, toxicity is high and the extremely difficult high concentrated organic wastewater of effectively processing, and seeks its important topic that to carry out the efficient method of processing be the outer field of water treatment of Present Domestic.Biological treatment is the inexpensive method of extensive treating refuse percolate.But, due to the high density NH that exists in percolate
3-N can suppress microbic activity, thereby has limited the efficient performance of biological treatment, and therefore many investigators are exploring the high-level oxidation technology of the pre-treatment before can be used as biological treatment or aftertreatment and easily realization in recent years.The characteristics of this method are environment not to be produced secondary pollution.Wherein, photoxidation and photocatalysis oxidation technique are developing direction, but this method is as pre-treatment, and its oxidant consumption is larger, and pH adjust more difficult, therefore be applicable to as the advanced treatment after biological treatment; The electro-chemical water treatment technology comprises that oxidative degradation and oxidation-reduction transform, and oxidative degradation is divided into again direct electrochemistry oxidative degradation and indirect oxidation degraded, and it is the systems engineering of a complexity.The electrochemical treatment method is applicable to as the pre-treatment before biological treatment, but By Electrocatalytic Oxidation remains and life-span short problem high in the catalysis electrode manufacturing cost, all has to be solved.Numerous studies show that promotes electrochemical treatment method high efficiency and the practical first-elected pulse power that adopts of measure, but makes its slower development because of complicacy high-power, the development of the low frequency pulse power.
Summary of the invention
The object of the invention is to overcome the existing pulse electrochemical defective that the middle pulse power exists that learns a skill, a kind of variable-frequency pulse electro-chemical water treatment process is provided, garbage filter liquefied ammonia-nitrogen or the trade effluent that contains ammonia-nitrogen are carried out ammonia-nitrogen process.
Technical solution of the present invention is: a kind of pulse electrochemical technique of removing garbage filter liquefied ammonia-nitrogen, its operational path is: percolate → variable-frequency pulse electrochemical process → anaerobic treatment → A/O biological treatment → advanced treatment → qualified discharge, or percolate → anaerobic treatment → A/O biological treatment → variable-frequency pulse electrochemical process → qualified discharge.
In above-mentioned pulse electrochemical operational path, described variable-frequency pulse electrochemical process comprises the processing condition of variable-frequency pulse electrochemical appliance and optimization thereof.
described variable-frequency pulse electrochemical appliance comprises electrolyzer and the variable-frequency pulse power supply that is connected with the battery lead plate of electrolyzer, the variable-frequency pulse power supply is arranged in power cabinet, the external three-phase 380V/50Hz of the input terminus of variable-frequency pulse power supply power supply, output terminal is that anode and negative electrode are derived, access respectively positive pole and the negative pole of the battery lead plate of the electrolyzer that matches, be provided with frequency on the power cabinet control panel, voltage and current is regulated turn-knob, described adjusting turn-knob is regulated in variable-frequency pulse electrochemical process condition and range, make the variable-frequency pulse electric current of its output have the electrical effect optimizational function.
Variable-frequency pulse electrochemical process condition is the battery lead plate spacing 25-30mm in electrolyzer; The power frequency 3-10kHz that arranges on the power cabinet control panel, unipolar voltage 3.5-6.5V, current density 4.5-8.5A/ (dm)
2Temperature of reaction＜50 ℃, reaction times 20-40min in electrolyzer are set in electrolyzer.
The battery lead plate that electrolyzer adopts is special ferrite high-silicon alloy plate, and the weight ratio that described ferrite high-silicon alloy plate contains Si is 0.8-1.0%, contain MnO
2Weight ratio be 0.3%.
Under above-mentioned variable-frequency pulse electrochemical process condition, produce electricity-Fenton (also claiming E-Fenton) oxidation, electrocatalysis direct oxidation (ECO) and indirect oxidation in electrolyzer system:
Under above-mentioned variable-frequency pulse electrochemical process condition, the anode in electrolyzer system produces electrocatalysis direct electrochemistry oxidation: ECO+NH
4 +-N → N
2↑+n H
2O；
Under above-mentioned variable-frequency pulse electrochemical process condition, the H that produces in electrolyzer system
2O
2The oxygenant that belongs to medium tenacity, self can produce oxygenizement, simultaneously H
2O
2And Fe
2+Fenton's reaction namely occurs in collision, generates strong oxidizer---hydroxyl radical free radical (HO):
Fe
2++H
2O
2→·OH+OH
-+Fe
3+，
2NH
3+6·OH→N
2↑+6H
2O，
Fe
3+Be reduced into again Fe on negative electrode
2+, so electricity-Fenton circulates repeatedly, and the ammonia-nitrogen that contains in percolate is by oxidation removal progressively;
Under above-mentioned variable-frequency pulse electrochemical process condition, the indirect oxidation that carries out in electrolyzer system: the Cl that contains in percolate
-Change HClO in electrolyzer into, reaction formula is as follows:
HClO+NH
4 +→N H
2Cl+H
++H
2O；
N H
2C1+HClO→NHCl
2+H
2O；
N H
2Cl+NHCl
2→N
2↑+3H
++3Cl
-；
Electricity-the Fenton oxidation that produces in above-mentioned variable-frequency pulse electrochemical process, electrocatalysis direct oxidation and indirect oxidation make the ammonia-nitrogen that contains in percolate change one after another nitrogen into and enter atmosphere.
The invention has the beneficial effects as follows: adopt the variable-frequency pulse electrochemical process that the ammonia-nitrogen of percolate is processed, under the variable-frequency pulse electrochemical process, because ammonia-nitrogen has obvious reducing property, can preferentially be removed, comprise electricity-Fenton oxidation, direct oxidation and indirect oxidation, the variable-frequency pulse electrochemical process can reach 70-100% to the clearance of ammonia-nitrogen, and unit power consumption is at 4-8Kwh/m
3Percolate, the water outlet NH3-N content after processing through full operational path is below 6mg/L, reached the emission standard of national GB16889-2008 " household refuse landfill sites pollution control criterion ", and the Processing Test data has good repeatability.
The electrolyzer of technique of the present invention has adopted ferrite high-silicon alloy plate, ferrite high-silicon alloy plate does not produce passive film and has electro catalytic activity under galvanic action, also have rational galvanic corrosion speed, thereby avoided that general steel plate electrode electro Chemical corrosion speed is too fast, common alloy steel plate electrode is without electro catalytic activity, easily passivation makes the drawbacks such as electrochemical reaction can not go on continuously; Because power supply has applied the variable-frequency pulse electrical signal, reaction on electrode off and on, not only have electric hammer effect, electrical effect, also help diffuse fluid, reduce concentration polarization, thereby reduce the unit power consumption for the treatment of refuse percolate and adjust the rational galvanic corrosion speed of ferrite high-silicon alloy plate, experimental results show that, unit power consumption reduces by 50% than the electrolysis of conventional DC power supply, galvanic corrosion Speed Reduction 75%.
Embodiment
Adopt the variable-frequency pulse electrochemical process that garbage filter liquefied ammonia-nitrogen is processed, the connecting mode of variable-frequency pulse electrochemical process and biochemical system can the water quality different according to percolate be selected.Described variable-frequency pulse electrochemical process comprises the processing condition of variable-frequency pulse electrochemical appliance and optimization thereof.
described variable-frequency pulse electrochemical appliance comprises electrolyzer and the variable-frequency pulse power supply that is connected with the battery lead plate of electrolyzer, the variable-frequency pulse power supply is arranged in power cabinet, the external three-phase 380V/50Hz of the input terminus of variable-frequency pulse power supply power supply, output terminal is that anode and negative electrode are derived, access respectively positive pole and the negative pole of the battery lead plate of the electrolyzer that matches, be provided with frequency on the power cabinet control panel, voltage and current is regulated turn-knob, described adjusting turn-knob is regulated in variable-frequency pulse electrochemical process condition and range, make the variable-frequency pulse electric current of its output have the electrical effect optimizational function.
Variable-frequency pulse electrochemical process condition is the battery lead plate spacing 25-30mm in electrolyzer; The power frequency 3-10kHz that arranges on the power cabinet control panel, unipolar voltage 3.5-6.5V, current density 4.5-8.5A/ (dm)
2Temperature of reaction＜50 ℃, reaction times 20-40min in electrolyzer are set in electrolyzer.
The battery lead plate that electrolyzer adopts is special ferrite high-silicon alloy plate, and the weight ratio that described ferrite high-silicon alloy plate contains Si is 0.8-1.0%, contain MnO
2Weight ratio be 0.3%.
The chemical expression of technique of the present invention is as follows:
O
2+2H
++2e
-→H
2O
2，
M
red+H
2O
2→M
ox+·OH+OH
-
2NH
3+6·OH→N
2↑+6H
2O
2Cl
-→Cl
2+2e
-，
Cl
2+H
2O→HClO+H
++Cl
-
HClO+NH
4 +→N H
2Cl+H
++H
2O
N H
2Cl+HClO→NHCl
2+H
2O
N H
2Cl+NHCl
2→N
2↑+3H
++3Cl
-
M in formula
red, M
oxBe reduction-state, oxidation state electrode.
Embodiment one
Garbage loading embeading factory of old-age group percolate intractability is larger, at first adopts the variable-frequency pulse electrochemical process to process, and significantly removes ammonia-nitrogen, and improves the C/N ratio of percolate, also effectively improves simultaneously its biodegradability, and then follow-up biochemical system is processed.Its operational path is: percolate → variable-frequency pulse electrochemical process → anaerobic treatment → A/O biological treatment → advanced treatment → qualified discharge.Technique Inlet and outlet water significant parameter such as table 1
The aged percolate technique of table 1 Inlet and outlet water parameter list
| Project | CODcr(mg/L) | BOD 5/CODcr | NH 3-N(mg/L) |
| The former water of percolate | 7560 | 0.13 | 2010 |
| The electrochemical treatment water outlet | 3250 | 0.27 | 113 |
| Water outlet after the anaerobic-aerobic biochemical treatment | 7 |
Mature landfill leachate is after adopting the variable-frequency pulse electrochemical process to process, and ammonia-nitrogen is removed more than 90%, BOD
5/ CODcr reaches 0.27, follow-up anaerobism+A/O biochemical system continuation processing, and ammonia-nitrogen can reach the emission standard of GB16889-2008 " household refuse landfill sites pollution control criterion ".
Embodiment two
The processing of embodiment two to as if the early stage percolate of garbage loading embeading factory, the intractability less, processing technology routine is: percolate → anaerobic treatment → A/O biological treatment → variable-frequency pulse electrochemical process → qualified discharge; Technique Inlet and outlet water significant parameter such as table 2
The early stage percolate technique Inlet and outlet water parameter list of table 2
| Project | CODcr(mg/L) | NH 3-N(mg/L) |
| The former water of percolate | 13600 | 1210 |
| Percolate water outlet after biochemical treatment | 798 | 47 |
| Water outlet after the variable-frequency pulse electrochemical treatment | 6 |
The early stage percolate of garbage loading embeading factory is through water outlet CODcr 798mg/L after biochemical treatment, NH
3-N 47mg/L, CODcr and NH
3-N removal effect is all better, then water outlet NH after processing through the variable-frequency pulse electrochemical process
3-N 6mg/L.
The garbage loading embeading factory relative intractability of early stage percolate is less, after the process biochemical treatment, ammonia-nitrogen removal effect is also better, then carries out advanced treatment through the variable-frequency pulse electrochemical process, and its water outlet can reach the emission standard of GB16889-2008 " household refuse landfill sites pollution control criterion ".
Claims (1)
1. pulse electrochemical technique of removing garbage filter liquefied ammonia-nitrogen, comprise anaerobic treatment, A/O biological treatment, it is characterized in that carrying out the variable-frequency pulse electrochemical pre-treatment before anaerobic treatment, A/O biological treatment, perhaps carry out variable-frequency pulse electrochemistry advanced treatment after anaerobic treatment, A/O biological treatment; The variable-frequency pulse electrochemical treatment comprises the variable-frequency pulse electrochemical appliance; The variable-frequency pulse electrochemical appliance comprises electrolyzer and the variable-frequency pulse power supply that is connected with the battery lead plate of electrolyzer, the variable-frequency pulse power supply is arranged in power cabinet, the external three-phase 380V/50Hz of the input terminus of variable-frequency pulse power supply power supply, output terminal is that anode and negative electrode are derived, access respectively positive pole and the negative pole of the battery lead plate of electrolyzer, be provided with frequency, voltage and current adjusting turn-knob on the power cabinet control panel; Battery lead plate in electrolyzer is ferrite high-silicon alloy plate, and the weight ratio that ferrite high-silicon alloy plate contains Si is 0.8-1.0%, contains MnO
2Weight ratio be 0.3%; Battery lead plate spacing 25-30mm in electrolyzer; The power frequency 3-10KHz that arranges on the power cabinet control panel, unipolar voltage 3.5-6.5V, current density 4.5-8.5A/ (dm)
2Temperature of reaction＜50 ℃, reaction times 20-40min in electrolyzer are set in electrolyzer.
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| CN102718364B (en) * | 2012-06-28 | 2013-07-31 | 常熟南师大发展研究院有限公司 | Step water purification system |
| CN104529046B (en) * | 2015-01-21 | 2016-08-17 | 中钢集团武汉安全环保研究院有限公司 | Process high concentrated organic wastewater RO concentrated solution equipment and group technology |
| CN109052806A (en) * | 2018-07-23 | 2018-12-21 | 安吉钰禾环保科技有限公司 | A kind of garbage leachate treatment device and method based on A/O- electrochemical oxidation-BAF group technology |
| CN111875061B (en) * | 2020-08-06 | 2021-04-20 | 江苏道同环境科技有限公司 | Recycling device and process for high-hardness nitrate wastewater |
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|---|---|---|---|---|
| CN1382647A (en) * | 2002-05-10 | 2002-12-04 | 清华大学 | Equipment for denitrifying and dephosphating sewage in integrated aerobic/anaerobic biologic fiter pool |
| CN1544365A (en) * | 2003-11-27 | 2004-11-10 | 武汉安全环保研究院 | Urban refuse sanitary landfill leachate disposing process |
| CN1587124A (en) * | 2004-09-14 | 2005-03-02 | 北京大学 | Garbage percolation liquid treating system and method |
| CN1931751A (en) * | 2006-10-25 | 2007-03-21 | 北京大学 | Combined process of treating azo dye effluent with high salinity |
| CN101041531A (en) * | 2006-03-20 | 2007-09-26 | 刘景峰 | Multiple combined technique for high concentration hard-degraded organic waste water treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4111970B2 (en) * | 2005-11-18 | 2008-07-02 | 三洋電機株式会社 | Water treatment equipment |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382647A (en) * | 2002-05-10 | 2002-12-04 | 清华大学 | Equipment for denitrifying and dephosphating sewage in integrated aerobic/anaerobic biologic fiter pool |
| CN1544365A (en) * | 2003-11-27 | 2004-11-10 | 武汉安全环保研究院 | Urban refuse sanitary landfill leachate disposing process |
| CN1587124A (en) * | 2004-09-14 | 2005-03-02 | 北京大学 | Garbage percolation liquid treating system and method |
| CN101041531A (en) * | 2006-03-20 | 2007-09-26 | 刘景峰 | Multiple combined technique for high concentration hard-degraded organic waste water treatment |
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Non-Patent Citations (1)
| Title |
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| JP特开2006-61910A 2006.03.09 |
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