CN101734817B - Method for treating organic chemical waste water - Google Patents
Method for treating organic chemical waste water Download PDFInfo
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- CN101734817B CN101734817B CN2009101868824A CN200910186882A CN101734817B CN 101734817 B CN101734817 B CN 101734817B CN 2009101868824 A CN2009101868824 A CN 2009101868824A CN 200910186882 A CN200910186882 A CN 200910186882A CN 101734817 B CN101734817 B CN 101734817B
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Abstract
The invention discloses a method for treating organic chemical waste water. In the method, after the pH value of the waste water is adjusted to 2.5-3.0, the organism which is hard to degrade is efficiently removed and the biochemical property of the waste water is enhanced through the aeration microelectrolysis, Fenton oxidization and coagulating sedimentation processes, and the Fe<2+> generated after the microelectrolysis reaction can be used for subsequent Fenton oxidization reaction, thereby reducing the treatment cost. The invention can be widely applied to treating various kinds of low concentration organic waste water which is hard to biodegrade, such as chemicals, pharmacy, and the like; and the treated water can directly reach the standard and be drained. The invention can also be used as a pretreatment method of the organic waste water with high concentration to improve the biochemical property of the waste water which is hard to biodegrade.
Description
Technical field
The present invention relates to a kind of method of handling organic chemical waste water.
Background technology
The annual great amount of wastewater that produces of chemical industry becomes a universally acknowledged difficult problem because of its salinity is high, toxicity is big, be difficult to biological degradation, and ecotope and HUMAN HEALTH are all had serious harm, also be China's pollution the most seriously, one of the most unmanageable trade effluent.The method of handling at present organic chemical waste water has a lot, as can adopting bioremediation, but contains the toxic substance that suppresses microorganism growth in the waste water, and then bioremediation is difficult to reach treatment effect preferably; Can also adopt aeration micro-electrolysis method, Fenton oxidation style, the aeration micro-electrolysis method carries out in iron charcoal reactor drum, general treatment of acidic wastewater; When being immersed in iron particle and charcoal particle in the acid waste water, because the difference in Electrode Potential between iron and the charcoal can form numerous little galvanic cell in the waste water; The iron that wherein current potential is low becomes anode; The charcoal that current potential is high becomes negative electrode, and electrochemical reaction takes place under acidic conditions, and its reaction process is following:
Anode (Fe): Fe-2e → Fe
2+
Negative electrode (C): 2H
++ 2e → 2 [H] → H
2
This micro-electrolysis reaction has produced Fe
2+And atom [H], atom [H] has high chemically reactive, can change some organic structure and characteristic in the waste water, makes effects such as organism generation chain rupture, open loop, and degradation of organic substances can improve the biodegradability of waste water.In iron charcoal reactor drum, implement aeration aerating and handle, then also following reaction can take place:
O
2+4H
++4e→2H
2O；
O
2+2H
2O+4e→4OH
-；
2Fe
2++O
2+4H
+→2H
2O+Fe
3+。
The OH that generates in the reaction
-Can improve the pH value of waste water, Fe
3+Can generate the big Fe of the polymerization degree (OH)
3Colloid flocculation agent, this flocculation agent can adsorb, condense the pollutent in the water effectively, thereby strengthen the decontamination effect improving to waste water.
To sum up, the aeration micro-electrolysis method has certain processing effect to the refractory organic in the waste water.The Fenton oxidation style then has significant effect for the processing of organic wastewater with difficult degradation thereby, and the Fenton reagent that adopts in the Fenton oxidation style is Fe
2+And H
2O
2, H
2O
2At Fe
2+Katalysis generate down hydroxyl radical free radical (OH) with high reaction activity, OH can make its degraded with most of organism effects in the waste water, simultaneously, Fe
2+Be oxidized to Fe
3+Produce coagulating sedimentation, remove the suspended substance in the waste water.Hydroxyl radical free radical in the Fenton oxidation style (OH) is an inorganic oxidizer the strongest except that element fluorine, can most of oxidation operations in the waste water be decomposed, so the Fenton oxidative treatment is organic effective, but needs Fe in the Fenton oxidation style
2+, production cost is high.
Summary of the invention
The purpose of this invention is to provide a kind of method that aeration micro-electrolysis method and Fenton oxidation style are handled organic chemical waste water of uniting, the treatment effect of this method is good and production cost is low.
For achieving the above object, the technical scheme that the present invention adopts is: a kind of method of handling organic chemical waste water may further comprise the steps:
(1) said waste water is adjusted to the pH value between 2.5-3.0;
(2) the pH value be 2.5-3.0 waste water with 0.8-1.2 rice/hour flow velocity through iron charcoal reactor drum, carry out micro-electrolysis reaction, carry out aeration in this iron charcoal reactor drum simultaneously;
(3) in step (2), add ydrogen peroxide 50 in the waste water of output, stir and carry out the Fenton oxidizing reaction;
(4) in the waste water after the Fenton oxide treatment, add liming, the pH value of waste water is adjusted into 8.5-9, adds the coagulant aids polyacrylamide then, carries out the coagulating sedimentation reaction, obtains supernatant.
Iron in the said iron charcoal reactor drum derives from the industrial waste iron filings, and the waste material iron filings are used earlier aqueous slkali soaking, to remove the dust and the oil stain on iron filings surface; Wash repeatedly with clear water then; Soak with acid solution again, get final product to remove surperficial sull of iron filings and rust stain, to clean repeatedly with clear water at last.
Iron charcoal mass ratio in the said iron charcoal reactor drum is 1: 1, iron particle grain size＜20 orders wherein, charcoal particle grain size＜100 orders.
Adding in the said iron charcoal reactor drum has catalyst oxidation copper, quickens iron charcoal micro-electrolysis reaction.
Because the present invention has adopted above technical scheme, its advantage is following: method of wastewater treatment of the present invention is united and has been adopted aeration micro-electrolysis method and Fenton oxidation style, the Fe that then produces behind the micro-electrolysis reaction
2+Can supply follow-up Fenton oxidation style to use, when the inventive method keeps water treatment effect well, can reduce processing cost.
Embodiment
Below further set forth the present invention.
At first introduce two indexs, BOD and COD, BOD are writing a Chinese character in simplified form of Biochemical Oxygen Demand; Biochemical oxygen demand refers to generally adopt five day time a time cycle; Organism in the water is because the biochemical action of mikrobe carries out oxygenolysis; The total quantity of the oxygen in water that consumes is also referred to as five-day BOD when making inorganicization of organism or aerification, and note is BOD
5, the value of BOD is big more, shows that organic pollution materials is many more in the water, pollutes also just serious more; COD is writing a Chinese character in simplified form of Chemical Oxygen Demand, refers to COD, when referring to strong oxidizer processing water sample; The oxidant content that is consumed, it is what a index of reducing substances in the expression water, the reducing substances in the water mainly refers to organism; Therefore, COD weighs what index of organic content in the water, and the COD value is big more; Explain that water body receives organic pollution serious more, the measuring method of COD can adopt potassium dichromate standard method, and principle is: in water sample, add a certain amount of SRM 935a and catalyst sulfuric acid silver; Reflux in the strongly-acid medium, the part SRM 935a is by an oxidisable substance reduction in the water sample, with the remaining SRM 935a of ferrous ammonium sulphate titration; Value according to the amount calculating COD that consumes SRM 935a is designated as COD
CrHow much organic pollutant in the talkative open fire of the ratio of biochemical oxygen demand BOD and chemical oxygen demand COD is that mikrobe can be decomposed if having, promptly indicate the biodegradability of waste water.The organic pollutant that mikrobe is difficult to decompose is bigger to the harm that environment causes.
BOD in the Chemical Manufacture waste water
5/ COD
CrBetween 0.05 to 0.15; Contain the toxic substance that suppresses microorganism growth; Belong to bio-refractory organic waste water, handle with physical chemistry method usually, this treatment process mainly comprises pH set-up procedure, the little electrolysis step of aeration, Fenton oxidation step, coagulating sedimentation step.Come the concrete treatment process of setting forth through an embodiment below:
(1) pH adjustment: the pH value of Chemical Manufacture waste water is adjusted to 2.5～3.0, the BOD of this wastewater from chemical industry
5/ COD
Cr=0.12;
(2) the little electrolysis of aeration: the waste water of pH value between 2.5-3.0 with the flow velocity of 0.8～1.2m/h through being filled with the reactor drum of iron charcoal; In the present embodiment; Iron charcoal reactor drum is arranged to two groups, and two groups of connections that are in series are through the two-stage micro-electrolysis reaction; Can improve organic degradation efficiency, obtain more Fe
2+And Fe
3+, go out under waste water is enterprising, implement aeration in each reactor drum simultaneously; GWR is 5: 1 (volume ratio), and aeration tube places the bottom of reactor drum, the adverse current aeration; The little electrolytic reaction process of aeration is referring to " background technology " part; Atom in the micro-electrolysis reaction [H] has high chemically reactive, a part of organism in can oxygenolysis waste water, the OH that reaction produces
-Can improve the pH value of waste water, part Fe
2+Can oxidized formation Fe
3+, be used for the coagulating sedimentation reaction, part Fe
2+Output is used for step Fenton oxidizing reaction down.Iron charcoal mass ratio was at 1: 1 o'clock, and the treatment effect of micro-electrolysis reaction is best, at this moment COD
CrClearance can reach 38.2%～42.5%, BOD
5/ COD
Cr=0.28.In micro-electrolysis reaction, iron receives the iron ion entering solution that corrosion becomes divalence, the tervalent iron ion of the oxidized formation of the iron ion of part divalence; Because iron ion has coagulation, there is a natural attraction between the sexes with the particulate of faint negative charge in iron ion and the waste water, forms more stable throw out (also being iron mud); Iron mud, organic degraded product, also have some granule foreigns together,, cover the iron carbon surface and form passive film as the reactant in the waste water; And the iron charcoal can't effectively be contacted; Then block micro-electrolysis reaction, cause reactor drum to use for some time aftertreatment effect to descend, therefore need carry out back flushing reactor drum; Can carry out back flushing through the G&W of certain pressure; The passive film of iron carbon surface or the reactant of covering are removed in flushing, and the direction of back flushing is opposite with the flow direction of waste water, can improve the treatment effect of reactor drum through back flushing.Also implemented aeration in the reactor drum; Not only can guarantee the dissolved oxygen concentration in the iron charcoal reactor drum through aeration; And the passive film that the motion of aeration gas flow makes the iron carbon surface form is brought in constant renewal in; That has improved reactor drum effectively utilizes volume, has increased the effect of electric field time between waste water and the iron charcoal, has also improved the processing power and the efficient of iron charcoal reactor drum.
Iron in the iron charcoal reactor drum can adopt the industrial waste iron filings, and iron filings should carry out pre-treatment before being packed into reactor drum, and the waste material iron filings are used earlier aqueous slkali soaking; Iron filings can be 3% NaOH solution soaking 30min at massfraction, to remove the dust and the oil stain on iron filings surface, wash repeatedly with clear water then; Soak with acid solution again; Can use massfraction is that 10% Hydrogen chloride soaks, and with sull and the rust stain of removing the iron filings surface, cleans repeatedly with clear water at last and gets final product.In reactor drum, the particle diameter of iron filings＜20 orders, the particle diameter of activated carbon granule＜100 orders to increase the specific surface area of iron charcoal reactor drum, improves the processing efficiency of waste water.In the little electrolysis step of aeration, adopt industrial waste iron filings and gac, then reduce production costs through " treatment of wastes with processes of wastes against one another " as raw material.In order to quicken iron charcoal micro-electrolysis reaction speed, also adding in the iron charcoal reactor drum has catalyst oxidation copper.
(3) Fenton oxidation: the waste water of from iron charcoal reactor drum, exporting, as stated, the OH that contains
-Make the pH value of waste water to rise, and the Fe that contains
2+Concentration be 180mg/L, satisfy in the Fenton oxidizing reaction Fe
2+Demand.Stir at the rotating speed of stirrer with 86r/min, the reaction times is 90min, H
2O
2When the throwing amount is 5mL/L, carry out the Fenton oxidizing reaction, the process of this oxidizing reaction is referring to " background technology " part, H
2O
2At Fe
2+Katalysis generate down hydroxyl radical free radical (OH) with high reaction activity, OH can make its degraded with most of organism effects in the waste water, can reach 69.5%～75.3%, BOD through this Fenton oxidizing reaction to the clearance of COD in the waste water under the normal temperature
5/ COD
Cr=0.33; Simultaneously, Fe
2+Be oxidized to Fe
3+Produce coagulating sedimentation, the suspended substance in the waste water is removed in absorption.This Fenton oxidizing reaction not only organism treatment effect to difficult degradation is good, and this reaction Fe that can directly utilize the aeration micro-electrolysis reaction to obtain
2+Thereby, reduce production costs.
(4) coagulating sedimentation: add liming in the waste water after the Fenton oxidation, adjustment pH value is to 8.5-9, and stirrer stirs with the rotating speed of 86r/min, and coagulating 30min generates colloid flocculation agent Fe (OH)
3, adding the PAM of coagulant aids 0.1% then, dosage is 5mg/L, stirrer stirs flocculation reaction 30min, Fe (OH) with the rotating speed of 16r/min
3Can adsorb, condense the pollutent in the water effectively, last waste water gets into tube settler and precipitates, the solid-liquid separate easily, and in water body, can not introduce new pollutent, precipitation process of coagulation COD
CrClearance can reach 37.1%～39.3%, and as far as the organic waste water of lower concentration, the supernatant that obtains is qualified discharge directly, as far as the organic waste water of high density, gets into follow-up biological treatment, further handles the back qualified discharge.
Use treatment process of the present invention that the factory effluent of chemical pharmaceutical enterprise is carried out sampling analysis, the essential property of Chemical Manufacture waste water: COD
Cr: 800-1600mg/L, pH are 10～12, saltiness 1%-5%, BOD
5/ COD
CrBetween 0.05 to 0.15, the waste water generation is 50m
3/ d.Result after method of the present invention is handled is as shown in the table:
| Project | The little bed electrolysis water inlet of iron charcoal pH value | Water inlet COD Cr | Water outlet COD Cr | Clearance % |
| Operating mode 1 | 2.9 | 831 | 34 | 95.9 |
| Operating mode 2 | 2.6 | 985 | 88 | 91.1 |
| Operating mode 3 | 2.9 | 939 | 82 | 91.3 |
| Operating mode 4 | 3.0 | 1060 | 95 | 91.0 |
| Operating mode 5 | 3.0 | 995 | 94 | 90.6 |
| Operating mode 6 | 2.5 | 964 | 85 | 91.2 |
Can find out from last table; The waste water that chemical industry synthesis pharmaceutical process produces is strong basicity, and saltiness is higher, and toxicity is big, be difficult to biological degradation; This waste water is through adjusting the pH value after suitable scope; Add the Fenton oxidation through the little electrolysis of aeration and add coagulation-settlement process, the COD clearance is more than 90%, and water outlet can reach national grade one discharge standard.The inventive method has the advantage that treatment effect is good, processing cost is low, wastewater biochemical property obviously improves; The present invention can be widely used in the processing of the organic waste water of all kinds of difficult for biological degradation lower concentrations such as chemical industry, pharmacy; Waste water after the processing is qualified discharge directly, also can be used as high density organic waste water pretreatment process and improve the biodegradability of waste water difficult for biological degradation.
Claims (4)
1. method of handling organic chemical waste water may further comprise the steps:
(1) said waste water is adjusted to the pH value between 2.5-3.0;
(2) the pH value be 2.5-3.0 waste water with 0.8-1.2 rice/hour flow velocity through iron charcoal reactor drum, carry out micro-electrolysis reaction, carry out aeration in this iron charcoal reactor drum simultaneously;
It is characterized in that:
(3) in step (2), add ydrogen peroxide 50 in the waste water of output, stir and carry out the Fenton oxidizing reaction;
(4) in the waste water after the Fenton oxide treatment, add liming, the pH value of waste water is adjusted into 8.5-9, adds the coagulant aids SEPIGEL 305 then, carries out the coagulating sedimentation reaction, obtains supernatant;
In above-mentioned steps (2), adding in the said iron charcoal reactor drum has catalyst oxidation copper, quickens iron charcoal micro-electrolysis reaction;
Said iron charcoal reactor drum is after handling waste water, and the iron carbon surface in this reactor drum can be covered by reactant, removes the reactant of this covering through the back flushing of gas or water, and the direction of this back flushing is opposite with the flow direction of waste water.
2. method according to claim 1; It is characterized in that: the iron in the said iron charcoal reactor drum derives from the industrial waste iron filings, and the waste material iron filings are used earlier aqueous slkali soaking, to remove the dust and the oil stain on iron filings surface; Wash repeatedly with clear water then; Soak with acid solution again, get final product to remove surperficial sull of iron filings and rust stain, to clean repeatedly with clear water at last.
3. method according to claim 1 and 2 is characterized in that: the iron charcoal mass ratio in the said iron charcoal reactor drum is 1: 1, iron particle grain size＜20 orders wherein, charcoal particle grain size＜100 orders.
4. method according to claim 1 is characterized in that: described iron charcoal reactor drum has two, and two said iron charcoal reactors in series connect.
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|---|---|---|---|
| CN2009101868824A CN101734817B (en) | 2009-12-31 | 2009-12-31 | Method for treating organic chemical waste water |
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|---|---|---|---|
| CN2009101868824A CN101734817B (en) | 2009-12-31 | 2009-12-31 | Method for treating organic chemical waste water |
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| CN101734817B true CN101734817B (en) | 2012-02-01 |
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