CN102531234A - Method for pretreatment of alkaline waste water through fenton oxidation - Google Patents
Method for pretreatment of alkaline waste water through fenton oxidation Download PDFInfo
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- CN102531234A CN102531234A CN2011104597272A CN201110459727A CN102531234A CN 102531234 A CN102531234 A CN 102531234A CN 2011104597272 A CN2011104597272 A CN 2011104597272A CN 201110459727 A CN201110459727 A CN 201110459727A CN 102531234 A CN102531234 A CN 102531234A
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- waste water
- alkaline waste
- alkaline
- fenton
- fenton oxidation
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Abstract
The invention discloses a method for pretreatment of alkaline waste water through fenton oxidation. The method comprises the following steps: at first, part of alkaline waste water is fetched, ferrous salt and H2O2 are added, part of alkaline waste water, ferrous salt and H2O2 enter into an oxidation pond for fenton oxidation reaction, the concentration ratio between H2O2 and COD in alkaline waste water is controlled within 1-1 to 1-10 by a concentration meter in alkaline waste water, and the concentration unit refers to mg/l; the fenton oxidation reaction time is 10 to 120 minutes, so that the PH value of waste water is reduced to be 3 to 4; the PH of alkaline waste water is 9 to 13, and the content of COD is 1000 to 1500 mg/l; oxidized waste water is mixed with untreated alkaline waste water in a primary settling tank according to the volume ratio being 1-1 to 1-5, and the PH value of the mixed waste water is 7 to 8. Under the condition that no sulphuric acid is added and the PH value is regulated through the adding of alkaline, the fenton oxidation reaction is achieved; and under the condition of the same treatment effect, the cost of acid-base drug is saved, and the operation intensity is reduced.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, be specifically related to a kind of method of utilizing Fenton (Fenton) reagent oxidation pre-treatment alkaline waste water.
Background technology
Fenton (Fenton) reagent is catalyzed oxidation reagent commonly used, and it is made up of ferrous salt and ydrogen peroxide 50, and when pH value was enough low, under the katalysis of ferrous ion, hydrogen peroxide can decompose generation (OH), thereby causes a series of chain reaction.It is following that Fenton reagent produces free-radical oxidn mechanism:
Fe
2++H
2O
2→Fe
3++(OH)+OH
- (1)
Fe
2++(OH)→Fe
3++OH
- (2)
Fe
3++H
2O
2→Fe
2++(HO
2)+H
+ (3)
(HO
2)+H
2O
2→O
2+H
2O+(OH) (4)
RH+(OH)→(R)+H
2O (5)
(R)+Fe
3+→R
++Fe
2+ (6)
R
++O2→ROO+→...→CO
2+H
2O (7)
Fe in the above-mentioned reaction
2+Play a part catalyzer, it and H
2O
2Between reaction very fast, generate very strong (OH) radical of oxidation capacity.When the ferric iron coexistence is arranged, because Fe
3+With H
2O
2Generate Fe lentamente
2+, follow Fe
2+Again with H
2O
2Reaction rapidly generates (OH), (OH) generates organic free radical (R) with organism RH reaction, and (R) further oxidation finally makes the fracture of organic constitution generation carbochain, is oxidized to carbonic acid gas and water, thus degradation of contaminant.
The Fenton oxidation technology has simple to operate, reacts characteristics such as quick, thereby has obtained extensive studies.But traditional Fenton oxidation need be carried out under acidic conditions; For alkaline waste water; Then elder generation is extremely acid through the pH that adds acid adjusting waste water, carry out oxidizing reaction again, and the wastewater pH of reacting after finishing is lower; Be will directly discharge or further biological treatment all need be under neutrallty condition, therefore then must add alkali transfers to neutrality with waste water.Thereby traditional Fenton oxidation treatment method needs the bronsted lowry acids and bases bronsted lowry of labor when handling alkaline waste water; Cause its industrialized application to receive bigger restriction; Thereby be necessary the Fenton oxidation treatment method is improved, do not consume bronsted lowry acids and bases bronsted lowry, thereby reduce the processing cost of Fenton oxidation; Simplified operating process, the Fenton oxidation technology is more widely used in industry.
At present; Document both domestic and external mainly concentrates on improvement raising and Fenton oxidation and other treatment technology couplings of the catalysis technique of Fenton oxidation technology and handles the waste water aspect for the report of Fenton oxidation treatment method; For example: Chinese invention patent CN1724420A proposes a kind of method of chemical oxidizing-biological biological filtering tank associating water treatment, and the COD that this method adopts Fenton reagent-biological aerated filter process to handle chemical plant secondary biochemical treatment wastewater effluent can reduce to 30mg/L.The disclosed treating printing and dyeing waste water by high pressure cavitation jet combined with fenton reagent of Chinese invention patent CN1899986 comprises that using acid for adjusting pH is 2.0～3.5; Add concentration and be respectively 0.009～0.015mol/L ferrous sulfate, and 0.1～0.15mol/L hydrogen peroxide; Use sodium hydroxide to regulate that wastewater pH is 8.0～10.0 after the oxide treatment again, add hydrogen peroxide, making concentration of hydrogen peroxide is 0.01～0.05mol/L, and using and being pumped into pressure is in 0.4～0.6Mpa cavitation device; Make dyeing waste water from the Fenton reagent oxidation pond to cavitation device, be back to the Fenton reagent oxidation pond from cavitation device again, circulation cavitation 8～14 times; To enter the coagulative precipitation tank flocculation separation through the waste water after the high pressure cavitation jet circular treatment, with flyash to flocculation sediment after clear liquid carry out adsorption treatment.This processing process is too complicated, needs to regulate pH repeatedly with a large amount of bronsted lowry acids and bases bronsted lowries, and dosing is big, lacks actual application value.The disclosed little water yield used water difficult to degradate deep purifying process for reclaiming of Chinese invention patent CN101254987 and for example; Add acid adjustment wastewater pH to 3～5; Get into the moving sulfuration bed of spray reaction tower,, use up again and help the Fenton catalytic oxidation to handle earlier with this waste water of micro-electrolysis treatment; Add alkali adjustment wastewater pH to 6.8～7.8, handle with the enhanced flocculation method then; Use the microwave catalysis oxidative treatment again; Use the UV photocatalysis treatment; Clarifying filter reaches the reuse water quality requirement.Same treating processes relative complex, the bronsted lowry acids and bases bronsted lowry dosage is big, and running cost is high.
Summary of the invention
The objective of the invention is to traditional Fenton oxidation treatment method; A kind of Fenton pretreatment process of new alkaline waste water is proposed; Be implemented in and do not consume bronsted lowry acids and bases bronsted lowry in the Fenton oxidation processes, thereby reduce processing cost, make the Fenton oxidizing reaction be easier to carry out alkaline waste water.
The object of the invention realizes through following technical scheme:
A kind of method of Fenton oxidation pre-treatment alkaline waste water comprises the steps and processing condition:
(1) gets the part alkaline waste water, add ferrous salt and H
2O
2, get in the oxidation pond and carry out the Fenton oxidizing reaction, with the densitometer in alkaline waste water, control H
2O
2With the ratio of the concentration of COD in the alkaline waste water be 1: 1～1: 10, concentration unit is mg/L; H
2O
2/ Fe
2+Mol ratio is 5: 1～1: 1; The Fenton oxidation time is 10～120 minutes, makes the pH value of waste water reduce between 3～4; The pH of said alkaline waste water is 9-13, and COD content is 1000-1500mg/L;
(2) waste water after the oxidizing reaction that step (1) is handled and untreated alkaline waste water are to mix in 1: 1～1: 5 at preliminary sedimentation tank by volume, make mixing afterwards the pH of waste water be 7-8.
For further realizing the object of the invention, said step (1) is controlled H with the densitometer in alkaline waste water
2O
2Be preferably 1: 1 with the ratio of the concentration of COD in the alkaline waste water～1: 2.5.
Said H
2O
2/ Fe
2+Mol ratio is preferably 3: 1～and 2: 1.
Said oxidation time is preferably 15～60 minutes.
Said alkaline waste water is preferably dyeing waste water.
Said waste water and untreated alkaline waste water after the oxidizing reaction that step (1) is handled is preferably 1: 2～1: 3 by volume at preliminary sedimentation tank.
Concentration unit is mg/L, with the densitometer in alkaline waste water, and control H
2O
2Be meant H with the ratio of the concentration of COD in the alkaline waste water
2O
2Calculate with the concentration of COD in alkaline waste water in the alkaline waste water.With H
2O
2With the ratio of the mass concentration of organism (COD) in the waste water be explanation in 1: 1, the COD of promptly intaking is the alkaline waste water of 1000mg/L, adds H
2O
2After, H
2O
2Mass concentration is 1000mg/L.
With respect to prior art, the present invention has following advantage:
To conventional Fenton oxide treatment alkaline waste water (pH is 9-13), need add a large amount of sulfuric acid and regulate pH to acid, carry out the Fenton oxidizing reaction again, need add a large amount of alkaline matters again after the reaction, wasted a large amount of soda acid medicaments, operate also cumbersome.The present invention adopts part waste water to add ferrous acidifying and Fenton oxidizing reaction; Waste water and part raw wastewater after this pH value of Fenton oxidizing reaction reduces mix; Regulate through the Fenton oxidizing reaction waste water and the ratio of not carrying out the waste water of Fenton oxidizing reaction; Can under the situation that does not add sulphur bronsted lowry acids and bases bronsted lowry adjusting pH, realize the Fenton oxidizing reaction; Under same treatment effect situation (ydrogen peroxide 50 and ferrous dosage and traditional ratio are approaching), save soda acid medicament expense usefulness, reduce manipulation strength and dosing kind.
In addition, the present invention is particluarly suitable for using in the pre-treatment of dyeing waste water, can reduce the COD load of water inlet, simultaneously, in also having reduced with waste water of basic printing and dyeing vitriolic consumption.
Embodiment
Below in conjunction with embodiment the present invention is described further, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1
Handle certain textile mills' alkalescence efflux wastewater, sewage character: COD is 1139mg/L, and pH is 9.23.With this textile mills' alkalescence efflux wastewater separated into two parts, a part is carried out the Fenton oxide treatment, and another part does not deal with, and is alkaline efflux wastewater, and wherein the volume ratio of Fenton sewage oxidation treatment and alkaline efflux wastewater is 1: 2.
The alkaline efflux wastewater of Fenton oxide treatment joins oxidation pond, and adds H
2O
2And Fe
2SO
4, H
2O
2Be oxygenant, Fe
2SO
4Be catalyzer, wherein, H
2O
2And Fe
2+Mol ratio be 3: 1; In mass concentration (concentration unit is mg/L), in every part of alkaline waste water, H
2O
2Add-on for control H
2O
2With the ratio of the mass concentration of organism (COD) in the waste water be that (for example: water inlet COD was the alkaline waste water of 1000mg/L, added H in 1: 1
2O
2After, H
2O
2Mass concentration is 1000mg/L), the pH of waste water was 3.23 in the oxidation pond, 30 minutes oxidation pond residence time; The Fenton reacted wastewater gets into preliminary sedimentation tank; The alkaline efflux wastewater that does not deal with at preliminary sedimentation tank and another part mixes, and the Fenton reacted wastewater was mixed with untreated alkaline efflux wastewater in 1: 2 by volume, through detecting; The pH of water outlet is 7.42, and the preliminary sedimentation tank residence time is 1 hour.Present embodiment Fenton oxidation treatment method is handled the treatment effect of waste water and is seen table 1.
Table 1 the present invention is used for the treatment effect of textile mills' alkaline waste water
| Former water | Fenton water outlet separately | Mix the back water outlet | |
| COD(mg/L) | 1139 | 472 | 712 |
| pH | 8.78 | 3.23 | 7.42 |
Annotate: separately the Fenton water outlet promptly refer to former water after Fenton handles not with former water blended waste water; Mix the back water outlet and refer to that former water handles back and former water blended waste water through Fenton.
Do not need in the present embodiment alkaline waste water is added sour adjustment of acidity; Can directly adopt ferrous sulfate and ydrogen peroxide 50 to make the pH value of waste water reduce to acidity (about pH=3); After the Fenton reaction, mix back pH with the former alkaline waste water of part and can reach weakly alkaline, thereby carry out the Fenton oxidation precipitation; Do not need other exogenously added alkali, and can carry out the biochemical treatment (appropriate pH of aerobic biochemical processing is 6-9) of follow-up catalytic oxidation.Therefore adopt this technology and traditional F enton technology relatively; Under the situation of identical ydrogen peroxide 50 and ferrous dosage and since just with the raw wastewater reaction of part, therefore begin to add ferrous can be with ydrogen peroxide 50 the time so that the pH of the waste water of reaction system drops to the Fenton optimum reaction condition about 3; After the reaction; Former water with part mixes again, utilizes the basicity of former water, need not add sodium hydroxide again.And traditional Fenton reaction is adding ydrogen peroxide 50 and ferrous in whole raw wastewaters the time, because the basicity in the waste water is too high; PH also will add sulfuric acid and be adjusted to the Fenton The optimum reaction conditions, about pH=3 about 6; After the reaction, add sodium hydroxide again, neutralization precipitation; Make the pH weakly alkaline simultaneously, handle thereby can carry out aerobic biochemical.In addition; Because the COD positive correlation of Fenton oxidation and waste water is therefore in Fenton preoxidation, under the situation of identical ydrogen peroxide 50 and ferrous add-on; No matter be and whole waste water reactions or elder generation and part waste water reaction that the final effect of handling is system roughly all.Therefore, the present invention is obtaining under the situation of same effect with traditional F enton oxidation, has saved the pharmaceutical quantities that begins to react sulfuric acid that adds and the sodium hydroxide that reacts the post neutralization needs.And conventional Fenton is for alkaline waste water; It is 3 yuan of/ton waste water that the sulfuric acid that need add and the medicament of sodium hydroxide are speculated amount; Therefore this technology can be saved 3 yuan of water per ton than common process aspect running cost, and cost saving greatly possesses the possibility that large-scale engineering is promoted.
Embodiment 2
Handle certain textile mills' high-concentration waste water (COD content is 1408mg/L, and pH is 9.63), adopt H
2O
2Be oxygenant, FeSO
4Be catalyzer, carry out the Fenton oxide treatment, operational condition is: get the part high-concentration waste water, add H
2O
2And FeSO
4, in mass concentration (concentration unit is mg/L), its H
2O
2With the ratio of the mass concentration of organism (COD) in this high-concentration waste water be 1: 2.5, H
2O
2/ Fe
2+Mol ratio be 2: 1; Oxidation pond pH is 4.17, and 15 minutes oxidation pond residence time, the waste water after the Fenton oxidizing reaction gets into preliminary sedimentation tank; At preliminary sedimentation tank; Waste water after the Fenton oxidizing reaction mixed with former high-concentration waste water in 1: 1 by volume, and water outlet pH is 7.63, and the preliminary sedimentation tank residence time is 1 hour.The Fenton oxidation treatment method of present embodiment is handled the treatment effect of waste water and is seen table 2.
Table 2 the present invention is used for the treatment effect of textile mills' high-concentration waste water
| Water inlet | The oxidation pond water outlet | Mix the back water outlet | |
| COD(mg/L) | 1408 | 428.66 | 904.00 |
| pH | 9.63 | 4.17 | 7.63 |
Do not need in the present embodiment alkaline waste water is added sour adjustment of acidity, can directly adopt ferrous sulfate and ydrogen peroxide 50 to make the pH value of waste water reduce to acidity, mix back pH with former alkaline waste water and can reach weakly alkaline, practice thrift reagent cost, and condition is provided for subsequent biological treatment.
Embodiment 3
Handle certain factory's reverse osmosis concentrated water (COD content is 123.56mg/L, and pH is 9.41) and add oxidation pond, adopt H
2O
2Be oxygenant, FeSO
4For catalyzer carries out the Fenton oxide treatment, operational condition is confirmed as: get the part high-concentration waste water and add oxidation pond, add H
2O
2And FeSO
4, in mass concentration (concentration unit is mg/L), H
2O
2With the ratio of the mass concentration of organism in the reverse osmosis concentrated water (COD) be 1: 1, H
2O
2/ Fe
2+Mol ratio is 2: 1, and oxidation pond water outlet pH is 4.22,30 minutes oxidation pond residence time.Then at preliminary sedimentation tank, mixed in 1: 4 by volume through the waste water and the former reverse osmosis concentrated water of Fenton oxide treatment, water outlet pH is 8.00, the preliminary sedimentation tank residence time is 1 hour.Present embodiment Fenton oxidation treatment method is handled the treatment effect of waste water and is seen table 3.
Table 3 the present invention is used for the treatment effect of certain factory's reverse osmosis concentrated water
| Water inlet | The oxidation pond water outlet | The preliminary sedimentation tank water outlet | |
| COD(mg/L) | 123.56 | 68.62 | 88.98 |
| pH | 9.41 | 4.22 | 7.50 |
Do not need in the present embodiment alkaline waste water is added sour adjustment of acidity; Can directly adopt ferrous sulfate and ydrogen peroxide 50 to make the pH value of waste water reduce to acidity; Mix back pH with former alkaline waste water and can reach weakly alkaline, practice thrift reagent cost, because reverse osmosis concentrated water often all is not biodegradable organism; After handling like this, but the waste water qualified discharge.
Claims (6)
1. the method for a Fenton oxidation pre-treatment alkaline waste water is characterized in that comprising the steps and processing condition:
(1) gets the part alkaline waste water, add ferrous salt and H
2O
2, get in the oxidation pond and carry out the Fenton oxidizing reaction, with the densitometer in alkaline waste water, control H
2O
2With the ratio of the concentration of COD in the alkaline waste water be 1:1～1:10, concentration unit is mg/L; H
2O
2/ Fe
2+Mol ratio is 5:1～1:1; The Fenton oxidation time is 10～120 minutes, makes the pH value of waste water reduce between 3～4; The pH of said alkaline waste water is 9-13, and COD content is 1000-1500mg/L;
(2) waste water after the oxidizing reaction that step (1) is handled mixes for 1:1～1:5 at preliminary sedimentation tank with untreated alkaline waste water by volume, and making the pH that mixes back waste water is 7-8.
2. according to the method for the said Fenton oxidation pre-treatment of claim 1 alkaline waste water, it is characterized in that said step (1) is controlled H with the densitometer in alkaline waste water
2O
2With the ratio of the concentration of COD in the alkaline waste water be 1:1～1:2.5.
3. according to the method for the said Fenton oxidation pre-treatment of claim 1 alkaline waste water, it is characterized in that said H
2O
2/ Fe
2+Mol ratio is 3:1～2:1.
4. according to the method for the said Fenton oxidation pre-treatment of claim 1 alkaline waste water, it is characterized in that said oxidation time is 15～60 minutes.
5. according to the method for the said Fenton oxidation pre-treatment of claim 1 alkaline waste water, it is characterized in that said alkaline waste water is a dyeing waste water.
6. according to the method for the said Fenton oxidation pre-treatment of claim 1 alkaline waste water, it is characterized in that said waste water and untreated alkaline waste water after the oxidizing reaction that step (1) is handled is 1:2～1:3 at preliminary sedimentation tank by volume.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304017A (en) * | 2013-06-28 | 2013-09-18 | 华南理工大学 | Treatment method for synchronously removing COD (Chemical Oxygen Demand) and rigidity of waste water |
| CN104609652A (en) * | 2015-01-08 | 2015-05-13 | 河北钢铁股份有限公司 | Coupling processing technology for steadily improving biodegradability of coking wastewater |
| CN105060577A (en) * | 2015-07-31 | 2015-11-18 | 湖州森诺膜技术工程有限公司 | Coating wastewater treatment technology |
| CN110240313A (en) * | 2019-06-17 | 2019-09-17 | 自然资源部第三海洋研究所 | The devices and methods therefor of Fenton processing refractory organic |
| CN110734172A (en) * | 2019-11-14 | 2020-01-31 | 广东石油化工学院 | preprocessing method for petroleum refining and petrochemical alkaline residue |
| CN111170506A (en) * | 2020-01-09 | 2020-05-19 | 北京恩菲环保股份有限公司 | Fenton oxidation treatment method for wastewater |
| CN112158941A (en) * | 2020-10-13 | 2021-01-01 | 石家庄新奥环保科技有限公司 | Fenton optimization oxidation treatment method for wastewater |
| CN112551744A (en) * | 2020-11-20 | 2021-03-26 | 联合环境技术(天津)有限公司 | Method for treating wastewater by utilizing acidic coagulated Fenton oxidation |
| CN113307421A (en) * | 2021-06-21 | 2021-08-27 | 南京理工大学 | Electrochemical oxidation auxiliary Fenton oxidation method for aldehyde chemical wastewater treatment |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304017A (en) * | 2013-06-28 | 2013-09-18 | 华南理工大学 | Treatment method for synchronously removing COD (Chemical Oxygen Demand) and rigidity of waste water |
| CN103304017B (en) * | 2013-06-28 | 2015-01-28 | 华南理工大学 | Treatment method for synchronously removing COD (Chemical Oxygen Demand) and rigidity of waste water |
| CN104609652A (en) * | 2015-01-08 | 2015-05-13 | 河北钢铁股份有限公司 | Coupling processing technology for steadily improving biodegradability of coking wastewater |
| CN105060577A (en) * | 2015-07-31 | 2015-11-18 | 湖州森诺膜技术工程有限公司 | Coating wastewater treatment technology |
| CN110240313A (en) * | 2019-06-17 | 2019-09-17 | 自然资源部第三海洋研究所 | The devices and methods therefor of Fenton processing refractory organic |
| CN110734172A (en) * | 2019-11-14 | 2020-01-31 | 广东石油化工学院 | preprocessing method for petroleum refining and petrochemical alkaline residue |
| CN111170506A (en) * | 2020-01-09 | 2020-05-19 | 北京恩菲环保股份有限公司 | Fenton oxidation treatment method for wastewater |
| CN112158941A (en) * | 2020-10-13 | 2021-01-01 | 石家庄新奥环保科技有限公司 | Fenton optimization oxidation treatment method for wastewater |
| CN112551744A (en) * | 2020-11-20 | 2021-03-26 | 联合环境技术(天津)有限公司 | Method for treating wastewater by utilizing acidic coagulated Fenton oxidation |
| CN113307421A (en) * | 2021-06-21 | 2021-08-27 | 南京理工大学 | Electrochemical oxidation auxiliary Fenton oxidation method for aldehyde chemical wastewater treatment |
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Application publication date: 20120704 |