CN100391871C - Anoxybiotic/aerobic two-section internal electrolysis organic waste water treating method - Google Patents
Anoxybiotic/aerobic two-section internal electrolysis organic waste water treating method Download PDFInfo
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Abstract
The invention relates to an anoxic/aerobic, two-stage, internal- electrolysis organic waste water treating method, fully mixing iron chips and activated carbon/copper chips in a certain mass ratio, and placing their mixture into a reactor, regulating waste water pH value and then adding the waste water into the reactor in the fixed solid-liquid ratio, firstly making anoxic internal electrolysis reation for a certain period of time and then making aerobic reaction for a certain period of time, adding alkali in the effluent water to make mixing coagulation settlement and discharging supernatant. And the treating mode can adopt a single- groove static flow mode or double-groove continous flow mode. And it fully uses redox reaction to degrade organic matters, and has stronger ability to degreade organic matters difficult to degrade and more remarkable decoloring effect.
Description
Technical field
The present invention relates to the method for electrolyzing organic waste water in a kind of anaerobic-aerobic two-part, interior electrolysis anoxic and aerobic two kinds of processing condition are combined,, handle the hardly degraded organic substance in the organic waste water by the mode of elder generation's reduction rear oxidation.Belong to water-treatment technology field.
Background technology
At present, along with the kind of sanitary sewage and trade effluent is increasing, composition is also complicated more, and wastewater treatment is also difficult day by day.Wastewater processing technology develops so far, and the waste water that some compositions are simple, biodegradability good, concentration is lower can be handled by the combination traditional technology, as biological treatment, coagulation, chemical precipitation etc.But a lot of waste water contain many hardly degraded organic substances, as phenol, alkyl benzene sulphonate (ABS), chlorophenol, agricultural chemicals, polychlorobiphenyl, polycyclic aromatic hydrocarbons, nitro-aromatic compound, dye well humic acid etc., cause that wastewater toxicity is big, the speed that is degraded by microorganisms is slow, intractability is big.Along with the enhancing of human environmental consciousness,, more and more tighter to the Toxic control that is discharged in the water body to the attention of water surrounding and to the Toxic understanding of enrichment in vivo.How to handle the important subject that these organic waste waters become the China environmental protection field effectively.Nearly two studies show that during the last ten years both at home and abroad, and high-level oxidation technology can more effectively be handled most of organic wastewater with difficult degradation thereby.
Interior electrolysis process is handled waste water as a kind of electrochemistry high-level oxidation technology, reduced investment, running cost are low, effective, the Wang Feng of Tongji University, Zhou Gongming etc. are applied to the processing (Techniques and Equipment for Environmental Pollution Control of Tao Pu manufacturing district combined sewage, October the 5th in 2004 rolled up, the 10th phase), the result shows: its COD, TP, NH
3The clearance of one N can reach 61.8%, 93.3%, 41.6% respectively, and is respond well, and processing unit is simple, no power consumption, expense are low, the treatment of wastes with processes of wastes against one another, and treatment effect is good, is a kind of more effective pretreatment process.But electrolysis also has some problems in finding simultaneously in practice: filler hardens easily, and sludge output is bigger, changes cumbersomely behind the anode consumption, and the device floor space is big when handling big flow waste water, invests high.Interior electrolysis tech is as a kind of technology of effective processing waste water, and treatment process exists the difference of anoxic and aeration condition.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the method for electrolyzing organic waste water in a kind of anaerobic-aerobic two-part is provided, can effectively handle organic wastewater with difficult degradation thereby, speed of reaction is fast, and running cost is low.
For realizing such purpose, in the novel combination type that the present invention adopts in the electrolysis process, iron filings and gac or iron filings and copper scale are pressed certain mass than thorough mixing, insert in the reaction unit.Wastewater pH is transferred to certain value, adds in the reaction unit according to the solid-to-liquid ratio of setting, aerobic reaction certain hour again behind the electrolytic reaction certain hour in the first anoxic, water outlet is the supernatant liquor discharging after adding the alkali coagulant precipitation.
Adopt earlier electrolysis in the anoxic in the inventive method, promptly under the condition of aeration not, the H of aquation in the electrolytic solution
+On negative electrode, be reduced into H
2And separate out, can generate [H] with very strong reducing power of nascent state in the reaction process, it can make some the oxidisability group in the hardly degraded organic substance be reduced.Be suppressed the back in reaction and adopt aerobic condition, increase galvanic corrosion power, on interior electrolysis cathode, be dissolved in the O in the solution
2Molecular ratio H
+Easier being reduced, O
2Under the katalysis of gac, the intermediate product that can produce a series of strong oxidizing property is (as [0
2 -], [H
2O
2], [OH] etc.) the oxidation hard-degraded substance.The present invention makes full use of the organism in oxidation and the reduction reaction processing organic wastewater with difficult degradation thereby, can improve treatment effect.
The present invention can adopt single groove passive flow mode and two kinds of treatment process of double flute Continuous Flow mode.
Single groove passive flow mode: establish supporting layer and perforated pipe at the bottom of the reactive tank, with iron filings and gac or iron filings and copper scale 1: 0.5～1: 2 thorough mixing of pressing mass ratio as filler, be filled in the reactive tank, the pH value of pending waste water is transferred to 3～8.5, according to the solid-to-liquid ratio of waste water and filler is to add in the reactive tank in 1: 1～1: 4, and the waste water flow velocity is 10～18mmmin
-1, waste water and filler are fully contacted carry out electrolytic reaction in the anoxic, behind reaction 30～60min, close outlet valve, open the aeration opening valve, waste water is reacted under aerobic condition, aeration rate is 50～100Lh
-1, behind 30～60min, with the waste water of discharging after adding the alkali coagulant precipitation, supernatant liquor discharging or further carry out biochemical treatment.
Double flute Continuous Flow mode: treatment process divides double flute to carry out, and the hypoxia response trench bottom is established supporting layer, and supporting layer and perforated pipe are established in aerobic slot reaction bottom.With iron filings and gac or iron filings and copper scale 1: 0.5～1: 2 thorough mixing of pressing mass ratio as filler, be filled in hypoxia response groove and the aerobic reactive tank, the pH value of pending waste water is transferred to 3～8.5, according to the solid-to-liquid ratio of waste water and filler is to add in the hypoxia response groove in 1: 1～1: 4, and the waste water flow velocity is 10～18mmmin
-1, waste water and filler fully being contacted carry out electrolytic reaction in the anoxic, effusive water is introduced in the aerobic reaction groove, adopts the aeration means that waste water is reacted under aerobic condition, and aeration rate is 50～100Lh
-1, behind 30～60min, with the waste water of discharging after adding the alkali coagulant precipitation, supernatant liquor discharging or further carry out biochemical treatment.
Iron filings of the present invention also can be the leftover bits of iron plate, iron wire or iron; Described copper scale also can be the leftover bits of copper sheet, copper wire or copper.
Advantage of the present invention is as follows:
1. electrolysis anoxic, aerobic condition in the present invention is used alternatingly.When degradation of organic substances, not only adopt reductive action, reduce the concentration of hardly degraded organic substance such as halohydrocarbon, reduced the toxicity of its generation, also adopted strong oxide group oxidation of organic compounds, and the product hydrophobicity is stronger, helps being removed by charcoal absorption or follow-up flocculation.The present invention is stronger than the ability of utilizing anoxic reductive action or aerobic oxidation effect processing hardly degraded organic substance separately, and decolorizing effect is more remarkable.
2. stop certain hour under anoxia condition, after speed of response is slowed down, change aerobic mode immediately into, fast reaction speed has been saved the time of interior electrolytic reaction, and the scum that generates in the whole process is reduced, and has reduced secondary pollution.
3. the leading portion reaction is under the anoxia condition in the reaction process, does not need the power of aeration, therefore obviously reduces than independent aerobic process processing costs.
4. the aeration mode in reaction process, the existence of oxygen can produce the intermediate material of a large amount of strong oxidizing properties at interior electrolysis cathode on the one hand, on the other hand, also play stirring action, prevented the filler caking, quicken the mass transfer between the organism and iron charcoal (copper) bed in the waste water, eliminated the denseization extreme difference in the catalyzed internal electrocatalysis reaction, accelerated speed of response.
5. treatment process is divided into two kinds, and wherein single groove passive flow technology can reduce floor space, and double flute continuous flow process floor space is big than passive flow technology, but processing power increases simultaneously.
Description of drawings
The structural representation of Fig. 1 single groove passive flow treatment unit for the present invention adopts.
Among Fig. 1,1 is recycling effluent mouth valve, and 2 is lift pump, and 3 is liquid meter, and 4 is reactive tank, and 5 is filler, and 6 is supporting layer, and 7 is perforated pipe, and 8 is the aeration opening valve, and 9 is gas meter, and 10 is aeration pump.
Fig. 2 adopts the structural representation of double flute Continuous Flow treatment unit for the present invention.
Among Fig. 2,2 is lift pump, and 3 is liquid meter, 4 is the reactive tank that uses as the anoxic groove, 5 is filler, and 6 is supporting layer, and 7 is perforated pipe, 8 is the aeration opening valve, 9 is gas meter, and 10 is aeration pump, and 11 is the aerobic reaction groove, 12 is the aerobic slot water outlet, and 13 is the water inlet valve of hypoxia response groove.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.
The present invention adopts single groove passive flow mode and two kinds of treatment process of double flute Continuous Flow mode.
When adopting single groove passive flow mode apparatus structure as shown in Figure 1, reactive tank 4 is made by pvc pipe, internal diameter 10cm, high 65cm, supporting layer 6 and perforated pipe 7 are installed in the bottom, can regulate flows by gas meter 9 and ventilate.With particle diameter be behind the waste iron filing of 0.3～0.5cm and gac (or copper scale) press mass ratio 1: 0.5～1: 2 weighing thorough mixing as filler 5, in the reactive tank 4 of packing into, the high 10cm of filler.Reactive tank should not design too high, in order to avoid influence the oxygen-transfer efficiency of aeration phase.The pH value of pending waste water is transferred to 3～8.5, is to add in the reactive tank in 1: 1～1: 4 according to the solid-to-liquid ratio of waste water and filler, closes aeration opening valve 8, opens outlet valve 1, and the waste water flow velocity is 10～18mmmin
-1, waste water and filler fully being contacted carry out electrolytic reaction in the anoxic, waste water is flowed out by water outlet after water pump 2 is back to reaction again in the device.Behind reaction 30～60min, close outlet valve 1, open aeration opening valve 8, make waste water be in reaction again under the aerobic condition, aeration rate is 50～100Lh
-1, behind 30～60min, no longer reflux after waste water is discharged by water outlet through water pump 2, the waste water of discharge after adding the alkali coagulant precipitation, supernatant liquor discharging or further carry out biochemical treatment.
When adopting double flute Continuous Flow mode apparatus structure as shown in Figure 2, this moment, reactive tank 4 used as hypoxia response groove 4.Hypoxia response groove 4 and aerobic reactive tank 11 are processed into by synthetic glass, the diameter 10cm of hypoxia response groove 4, and height is 40cm, aerobic reaction groove 11 is of a size of 15 * 10 * 25cm
3, hypoxia response groove 4 bottoms are provided with supporting layer 6, are filled with Fe/C filler or Fe/Cu filler, and aerobic reaction groove 11 bottoms are provided with supporting layer 6 and perforated pipe 7, can regulate flow by gas meter 9 and ventilate.With behind iron filings and gac or iron filings and copper scale press mass ratio 1: 0.5～1: 2 thorough mixing as filler, be filled in hypoxia response groove 4 and the aerobic reactive tank 11, all packing material sizes are between 0.3～0.5cm.The pH value of pending waste water is transferred to 3～8.5, is to add in the hypoxia response groove in 1: 1～1: 4 according to the solid-to-liquid ratio of waste water and filler.Waste water rises to the top of hypoxia response groove 4 through water pump 2, is 10～18mmmin with flow velocity
-1Enter hypoxia response groove 4, waste water and filler are fully contacted carry out electrolytic reaction in the anoxic, can regulate the water inlet flow velocity by liquid meter 3.For increasing the duration of contact of waste water and filler, hypoxia response groove more than 4 is designed to the tower shape, according to the residence time design tower height of waste water in the hypoxia response groove, does not reflux, to reduce processing costs.Waste water is introduced in the aerobic reaction groove 11 by the bottom of hypoxia response groove 4, by aeration pump 10 aerations, waste water is reacted under aerobic condition in the groove, aeration rate is 50～100Lh
-1, behind 30～60min, waste water is flowed out by aerobic slot water outlet 12, the waste water of discharge after adding the alkali coagulant precipitation, supernatant liquor discharging or further carry out biochemical treatment.
The following example 1-13 is with single groove passive flow technology advanced treatment of landfill leachate of the present invention
Waste water is taken from the percolate of the old port of Shanghai City waste landfill yard after the mineralized waste bed is handled, and COD is 538mgL
-1Waste water in inner electrolyser respectively anoxic and aeration state respectively stop 30min, the COD value of supernatant liquor is measured in water outlet after adding the alkali sedimentation.
The different initial pH value of embodiment 1-4 are to the influence of COD clearance
Regulating the initial pH to 3.0 of percolate (embodiment 1), 5.0 (embodiment 2), 7.0 (embodiment 3), 8.5 (embodiment 4) with acid, is 1: 2 with solid-to-liquid ratio, and aeration rate is 100Lh
-1Test, clearance is as shown in table 1:
The different initial pH value of table 1 are to the influence of percolate COD clearance (%)
Along with reducing of wastewater pH, the COD clearance increases.Find also in the research that when water inlet pH was 5.0, treatment effect was better, and water outlet pH is generally about 8.0, this will significantly reduce the consumption of alkali when adding alkali and regulating, and this is a comparatively economic water inlet pH initial value.
Embodiment 5-8: the influence of different solid comparison COD removal effect
To initial pH is 5.0 waste water, and aeration rate is 100Lh
-1, be respectively with solid-to-liquid ratio: test 1: 1 (embodiment 5), 1: 2 (embodiment 6), 1: 3 (embodiment 7), 1: 4 (embodiment 8).The result is as shown in table 2:
The influence of table 2 different solid comparison percolate COD clearance (%)
Solid-to-liquid ratio reduces, and removal effect descends, and this is that the micro-electrolysis reaction in the unit waste water reduces, and makes the water outlet deteriorating water quality because along with the reducing of solid-to-liquid ratio, the contact area of iron filings gac and waste water reduces.And in test, solid-to-liquid ratio is that the COD removal effect of 1: 1 and 1: 2 is more or less the same, and is 1: 2nd so adopt solid-to-liquid ratio, economical rationality.
Embodiment 9-12: different aeration rates are to the influence of removal effect
Regulating water inlet pH is 5.0, is 1: 2 with solid-to-liquid ratio, regulates aeration rate and is respectively 0Lh
-1(embodiment 9), 50Lh
-1(embodiment 10), 100Lh
-1(embodiment 11), 150Lh
-1Test (embodiment 12).Test-results is as shown in table 3:
The different aeration rates of table 3 are to the influence of percolate COD clearance (%)
Result of study shows that under acidity, aerobic condition, electrolytic reaction speed in can improving increases water treatment effect.
Embodiment 13: single groove passive flow technology of the inventive method with existing two kinds in the comparison of electrolysis process advanced treatment of landfill leachate.
Electrolysis process has two kinds in existing: (1) interior electrolytic process is under the anoxia condition always.Adopt Fig. 1 reaction unit, aeration not in the whole process, regulating water inlet pH is 5.0, solid-to-liquid ratio is 1: 2, after anoxic stopped reaction 60min, the adsorbable organism halogen (AOX) in mensuration percolate COD and the percolate was to represent the wherein concentration of toxic organic compound matter.(2) interior electrolytic process is under the aerobic condition always.Adopt Fig. 1 reaction unit, water inlet pH is 5.0, and solid-to-liquid ratio is 1: 2, aeration always, and the aeration flow is 100Lh
-1, behind the aerobic stop reaction 60min, measure COD and AOX.Under the top condition of result and method of the present invention (3), the pH of promptly intaking is 5.0, and solid-to-liquid ratio is 1: 2, and the aeration flow is 100Lh
-1The result relatively.Percolate water inlet COD is 538mgL
-1, adsorbable organic halogen is 9.98ppm.The result shows that the inventive method is the highest to the COD clearance, and is close with method (1) to the AOX clearance, sees Table 4:
Electrolysis process was to the influence of percolate COD and AOX clearance (%) in table 4 was different
| Index | Method (1) | Method (2) | The inventive method (3) |
| COD | 69 | 74 | 83.1 |
| AOX | 73.1 | 54.2 | 71 |
Embodiment 14: with single groove passive flow art breading methylenum coeruleum waste water of the present invention
Adopt the reaction unit of Fig. 1, filler is respectively by iron filings and copper scale mass ratio and mixed in 1: 1,1: 2,2: 1,1: 0 on the supporting layer, and iron filings and copper scale are all saturated before experiment, and laboratory preparation methylenum coeruleum concentration is 100mgL
-1, regulating initial pH on wastewater is 3.0, the aeration flow is 100Lh
-1, be waste water to be added in the reaction unit in 1: 2 with solid-to-liquid ratio.Anoxic and aeration state respectively stop 30min respectively in inner electrolyser, and water outlet is got supernatant liquor after adding the alkali coagulant precipitation stand-by.By methylenum coeruleum the visible region maximum absorption wavelength (λ=664nm) locates to measure the colourity of methylenum coeruleum waste water, and chroma removal rate is shown in Table 5:
The different Fe-Cu mass ratioes of table 5 are to the influence of methylenum coeruleum chroma removal rate (%)
Embodiment 15-16: with double flute continuous flow process Treatment of Cyanide-containing Wastewater of the present invention
Waste water is taken from Minhang District chemical plant, Shanghai City Workshop Production waste water, and the initial COD of waste water is 2937mgL
-1, pH is 8.5, does not regulate.Waste water is 15mmmin with the linear velocity
-1Enter the anoxic groove, enter aerobic slot after the anoxic concentrated flow goes out, aeration rate is 50Lh in the groove
-1, waste water is 15mmmin with the linear velocity by aerobic slot
-1Flow out, after adding the alkali coagulant precipitation, discharge.
Place iron filings and gac on the anoxic groove supporting layer, mass ratio is 2: 1, and the aerobic slot supporting layer is placed iron filings and gac, and mass ratio is 2: 1 (embodiment 15), and filtrate is all saturated before experiment.Recording discharging water outlet COD behind continuous flow process is 446mgL
-1, the COD clearance is 84.8%.
Place iron filings and gac on the anoxic groove supporting layer, mass ratio is 2: 1, and the aerobic slot supporting layer is placed iron filings and copper scale, and mass ratio is 2: 1 (embodiment 16), and filtrate is all saturated before experiment.Recording discharge water COD behind continuous flow process is 589mgL
-1, the COD clearance is 79.9%.
Claims (2)
1. the method for electrolyzing organic waste water in the anaerobic-aerobic two-part, it is characterized in that adopting double flute Continuous Flow mode, the hypoxia response trench bottom is established supporting layer, the aerobic reaction trench bottom is established supporting layer and perforated pipe, with iron filings and gac or iron filings and copper scale 1: 0.5～1: 2 thorough mixing of pressing mass ratio as filler, be filled in hypoxia response groove and the aerobic reactive tank, the pH value of pending waste water is transferred to 3～8.5, according to the solid-to-liquid ratio of waste water and filler is to add in the hypoxia response groove in 1: 1～1: 4, and the waste water flow velocity is 10～18mmmin
-1, waste water and filler are fully contacted carry out electrolytic reaction in the anoxic, behind reaction 30～60min, waste water is introduced in the aerobic reaction groove, adopt the aeration means that waste water is reacted under aerobic condition, aeration rate is 50～100Lh
-1, behind 30～60min, with the waste water of discharging after adding the alkali coagulant precipitation, supernatant liquor discharging or further carry out biochemical treatment.
2. the method for electrolyzing organic waste water in the anaerobic-aerobic two-part, it is characterized in that adopting single groove passive flow mode, with iron filings and gac or iron filings and copper scale 1: 0.5～1: 2 thorough mixing of pressing mass ratio as filler, being filled in the bottom is provided with in the reactive tank of supporting layer and perforated pipe, the pH value of pending waste water is transferred to 3～8.5, according to the solid-to-liquid ratio of waste water and filler is to add in the reactive tank in 1: 1～1: 4, and the waste water flow velocity is 10～18mmmin
-1, waste water and filler are fully contacted carry out electrolytic reaction in the anoxic, behind reaction 30～60min, close outlet valve, open the aeration opening valve, waste water is reacted under aerobic condition, aeration rate is 50～100Lh
-1, behind 30～60min, with the waste water of discharging after adding the alkali coagulant precipitation, supernatant liquor discharging or further carry out biochemical treatment.
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| CN102424473A (en) * | 2011-10-20 | 2012-04-25 | 天津工业大学 | Method for degrading chlorinated organic pollutant by separated electrocatalysis of microorganism |
| CN103253742A (en) * | 2013-05-13 | 2013-08-21 | 苏州有色金属研究院有限公司 | Multi-element internal electrolysis filler and preparation method thereof |
| CN107555701B (en) * | 2016-06-30 | 2020-09-29 | 鞍钢股份有限公司 | Low-cost coking wastewater treatment method |
| CN106477706A (en) * | 2016-12-14 | 2017-03-08 | 盐城工学院 | Method and the processing method of waste water from dyestuff that a kind of methylenum careuleum is faded |
| CN107619156A (en) * | 2017-10-16 | 2018-01-23 | 哈尔滨工业大学 | A kind of light electrolysis coupling anoxic biological reaction apparatus and the method using device processing coal gas wastewater aldehydes matter |
| CN107879473B (en) * | 2017-11-14 | 2021-05-18 | 东华大学 | Method for improving biological denitrification treatment efficiency of industrial wastewater |
| CN108467089B (en) * | 2018-02-13 | 2021-02-12 | 西安工程大学 | Pretreatment system and pretreatment method for refractory industrial wastewater |
| CN111634994B (en) * | 2020-06-11 | 2022-07-05 | 武汉轻工大学 | Reactor, system and method for improving biodegradability of refractory organic wastewater |
| CN111634984A (en) * | 2020-06-11 | 2020-09-08 | 武汉轻工大学 | Pretreatment system and method for organic industrial wastewater difficult to biodegrade |
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