CN103121746A - Method for treating wastewater by complexly activating persulfate - Google Patents
Method for treating wastewater by complexly activating persulfate Download PDFInfo
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- CN103121746A CN103121746A CN2013100894442A CN201310089444A CN103121746A CN 103121746 A CN103121746 A CN 103121746A CN 2013100894442 A CN2013100894442 A CN 2013100894442A CN 201310089444 A CN201310089444 A CN 201310089444A CN 103121746 A CN103121746 A CN 103121746A
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- waste water
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- organic waste
- peroxydisulfate
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Abstract
The invention relates to a method for treating wastewater by complexly activating persulfate. The method comprises the following steps of: adding ferroferric oxide or alpha-FeOOH or SBA-15 loaded copper iron oxide serving as catalyst and persulfate to organic wastewater to obtain reaction liquid; and treating the organic wastewater on the condition of an external electric field. According to the method disclosed by the invention, the solid catalyst is easy to recycle, so that the effective solid-liquid is ensured after the treatment, and the reuse characteristic of the catalyst is high. After the solid catalyst is added, the reaction pH value range is greatly expanded, so that the reaction can be carried out under nearly neutral condition, and the subsequent treatment processes are reduced. The solid catalyst can be used for efficiently activating persulfate in the system, the process operation is simple and easy to carry out, and the removing effect is good.
Description
Technical field
The invention belongs to field of waste water treatment, particularly a kind of multiplicity reactivation peroxydisulfate is processed the method for organic waste water.
Background technology
Industrial expansion has caused more and more serious ambient water to pollute, and in water body, mankind itself's health in a large amount of pollutent serious threats.High-level oxidation technology refers to the organic pollutant in water is converted into the small-molecule substance of low toxicity, readily biodegradable by chemistry or physicochemical method, is perhaps CO with the direct mineralising of organic pollutant
2, H
2O and other inorganics.High-level oxidation technology is considered to utilize the extremely strong hydroxyl radical free radical of the oxidation capacity that produces in its process with pollutant oxidation usually.In recent years, the treatment technology that produces the sulfate radical free radical based on the activation persulphate receives publicity day by day, heterogeneous activation persulphate technology has wherein overcome separation of metal ions in the homogeneous system, has reclaimed difficult shortcoming, has reduced the impact of metal ion on water outlet.But heterogeneous activating technology is had relatively high expectations to catalyzer, only has the catalyzer of special preparation to produce living radical by efficient activation persulphate.The electrochemistry wastewater processing technology is a kind of environmentally friendly technology, and especially, electric field can promote the conversion of catalyst active center's metal different valence state, realize catalyzer to the efficient activation of persulphate, and catalyzer can reuse.
Summary of the invention
For the present situation in background technology, the invention provides a kind of multiplicity reactivation peroxydisulfate and process the method for organic waste water, technical scheme is as follows: Z 250 or alpha-feooh or SBA-15 supported copper ferriferous oxide are added in organic waste water as catalyzer and peroxydisulfate, obtain reaction solution, under the extra electric field condition, organic waste water is processed.
As preference:
The electric current of described extra electric field is 0.5～2.0A.
The dosage of described catalyzer is 0.1g/L～1g/L.
Described peroxy-disulfuric acid salt concn is 3mmol/L～10mmol/L.
The pH value of described reaction solution is 3～10.
The present invention is based on use the heterogeneous activation persulphate of solid catalyst technology to catalyzer require high, the deficiencies such as common metal oxide or metal oxide-loaded activation effect are limited, pass through extra electric field, promote the conversion of catalyst active center's metal different valence state, realize that typical catalyst is to the efficient activation of persulphate.The present invention has simultaneously overcome homogeneous catalyst and has separated in water and reclaim difficult shortcoming, has realized the recycling of catalyzer.And this method can be reacted under the pH value condition that approaches neutrality, has greatly widened the pH scope of reaction, has reduced subsequent processing steps.
The present invention compares with homogeneous activation persulphate technology, and metal oxide or metal oxide supporting catalyst are not had particular requirement, and they all can efficiently activate persulphate under electric field action.And catalyzer is easy to reclaim, effective solid-liquid separation after having guaranteed to process, and catalyzer can reuse, and metal dissolving is low, has reduced the impact of metal ion on water outlet.
The beneficial effect of the inventive method is:
1, catalyzer is not had particular requirement, existing plain metal oxide compound or metal oxide supporting catalyst all can.
2, solid catalyst has been widened the pH value in reaction scope greatly, and reaction can reacting near under neutrallty condition, reduce subsequent treatment process.
3, solid catalyst is easy to reclaim, effective solid-liquid separation after having guaranteed to process, and the catalyzer reusing is high.
4, this technological operation is simple, and removal effect is better.
Embodiment
The present invention is take medicine and use in personal care category (PPCPs) and azoic dyestuff pollutant as typical organic waste water.PPCPs class waste water comprises various chemical substances, owing to using in a large number and continually in daily life, causes PPCPs to form false persistence phenomenon.Wherein the drug class material owing to not absorbed fully by human body or animal, is exposed in environment, and the mankind's health and existence is caused disadvantageous effect.Azoic dyestuff is present most widely used synthetic dyestuff and is difficult to be biodegradable.Azoic dyestuff has toxicity and carinogenicity, and this makes the problem that is treated as the society extensive concern of waste water from dyestuff.Therefore, select hypolipidemic clofibric acid and azoic dyestuff orange beta-naphthol respectively as the representative of PPCPs and dyestuff contaminant in embodiment.
The invention will be further described below by embodiment, illustrates outstanding feature of the present invention and marked improvement, only is the present invention is described and never is limited to the present invention.
Embodiment 1: in this embodiment, choosing SBA-15 supported copper ferriferous oxide is catalyzer, and persulphate is oxygenant, and clofibric acid solution is simulation PPCPs waste water.Contrasted catalyzer and activated separately persulphate (1), electrolysis (2) and catalyzer activate persulphate (3) three systems to the degraded of clofibric acid under current field condition separately.Activate separately in the persulphate system at catalyzer, after reaction 60min, the clofibric acid clearance is only 6.7%.In independent electrolysis system, the clearance of clofibric acid reaches 66.4%.In the heterogeneous activation persulphate of catalyzer system, clofibric acid almost can be removed (99.7%) fully under current field condition.Detailed operational condition and result are as follows:
One, operational condition
(1) catalyzer activates separately persulphate
Clofibric acid strength of solution: 25mg/L
Clofibric acid wastewater volume: 200mL
PH value: 6.5
Peroxy-disulfuric acid salt concn: 10mmol/L
Catalyst amounts: 0.5g/L
(2) independent electrolysis system
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: titanium plate plate electrode
Electrode specification: 5 * 11.9cm
Clofibric acid strength of solution: 25mg/L
Clofibric acid wastewater volume: 200mL
PH value: 6.5
Power supply mode: direct current, 1A
(3) the heterogeneous activation persulphate of catalyzer system under current field condition
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: titanium plate plate electrode
Electrode specification: 5 * 11.9cm
Clofibric acid strength of solution: 25mg/L
Clofibric acid wastewater volume: 200mL
PH value: 6.5
Catalyst amounts: 0.5g/L
Peroxy-disulfuric acid salt concn: 10mmol/L
Power supply mode: direct current, 1A
Two, experimental result:
Embodiment 2: in this embodiment, choosing SBA-15 supported copper ferriferous oxide is catalyzer, and persulphate is oxygenant, and clofibric acid solution is simulation PPCPs waste water.Contrasted the impact of different pH condition on the clofibric acid clearance, obtained respectively the clearance of clofibric acid under acid (pH3) and alkalescence (pH9) condition.Under the clearance of this embodiment explanation clofibric acid under alkaline condition and acidic conditions, the clearance of clofibric acid is suitable, uses this kind system greatly to widen the pH value in reaction scope.Detailed operational condition and result are as follows:
One, operational condition:
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: titanium plate plate electrode
Electrode specification: 5 * 11.9cm
Clofibric acid strength of solution: 25mg/L
Clofibric acid wastewater volume: 200mL
PH value: 6.5
Peroxy-disulfuric acid salt concn: 10mmol/L
Catalyst amounts: 0.5g/L
Power supply mode: direct current, 1A
Two, experimental result:
Embodiment 3: in this embodiment, choosing SBA-15 supported copper ferriferous oxide is catalyzer, and persulphate is oxygenant, and clofibric acid solution is simulation PPCPs waste water.Be to have obtained the clearance of clofibric acid under 0.5A and 2A condition in strength of current respectively.This embodiment illustrates that different current condition all have promoter action to reaction, and the higher promoter action of strength of current is more remarkable.Detailed operational condition and result are as follows:
One, operational condition:
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: titanium plate plate electrode
Electrode specification: 5 * 11.9cm
Clofibric acid strength of solution: 25mg/L
Clofibric acid wastewater volume: 200mL
PH value: 6.5
Peroxy-disulfuric acid salt concn: 10mmol/L
Catalyst amounts: 0.5g/L
Two, experimental result:
Embodiment 4: in this embodiment, choosing copper ferriferous oxide load SBA-15 is catalyzer, persulphate is oxygenant, and clofibric acid solution for simulation PPCPs pollutent, is to have obtained the clearance of clofibric acid under 0.1g/L and 1.0g/L condition at catalyst amounts respectively.Detailed operational condition and result are as follows:
One, operational condition:
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: titanium plate plate electrode
Electrode specification: 5 * 11.9cm
Clofibric acid strength of solution: 25mg/L
Clofibric acid wastewater volume: 200mL
Peroxy-disulfuric acid salt concn: 10mmol/L
Power supply mode: direct current, 1A
Two, experimental result:
Embodiment 5: in this embodiment, choosing commercial metals oxide compound Z 250 (Fe3O4) is catalyzer, and persulphate is oxygenant, and orange II is dye wastewater.Detailed operational condition and result are as follows:
One, operational condition:
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: stainless steel flat plate electrode
Electrode specification: 5 * 11.9cm
Orange II concentration: 50mg/L
Orange II wastewater volume: 400mL
Peroxy-disulfuric acid salt concn: 8.4mmol/L
Z 250 concentration: 0.5g/L
Orange II initial pH value: 3
Power supply mode: direct current, 1A
Embodiment 6: in this embodiment, choosing commercial metals oxide needle iron ore (alpha-feooh) is catalyzer, and persulphate is oxygenant, and orange II is dye wastewater.By the orange II clearance under the contrast different pH condition, find all can obtain the clearance of 90% left and right in the scope of pH3～10.Illustrate and use this kind wastewater treatment system greatly to widen the pH value scope of reaction.Detailed operational condition and result are as follows:
One, operational condition:
Anode: Ti/RuO
2-IrO
2Plate electrode
Negative electrode: stainless steel flat plate electrode
Electrode specification: 5 * 11.9cm
Orange II concentration: 50mg/L
Orange II wastewater volume: 400mL
Peroxy-disulfuric acid salt concn: 8.4mmol/L
Catalyst amounts: 0.5g/L
Power supply mode: direct current, 0.5A
Two, experimental result:
Claims (5)
1. a multiplicity reactivation peroxydisulfate is processed the method for organic waste water, it is characterized in that: Z 250 or alpha-feooh or SBA-15 supported copper ferriferous oxide are added in organic waste water as catalyzer and peroxydisulfate, obtain reaction solution, under the extra electric field condition, organic waste water is processed.
2. multiplicity reactivation peroxydisulfate as claimed in claim 1 is processed the method for organic waste water, and it is characterized in that: the electric current of described extra electric field is 0.5～2.0A.
3. multiplicity reactivation peroxydisulfate as claimed in claim 1 is processed the method for organic waste water, and it is characterized in that: the dosage of described catalyzer is 0.1g/L～1g/L.
4. multiplicity reactivation peroxydisulfate as claimed in claim 1 is processed the method for organic waste water, and it is characterized in that: described peroxy-disulfuric acid salt concn is 3mmol/L～10mmol/L.
5. multiplicity reactivation peroxydisulfate as claimed in claim 1 is processed the method for organic waste water, and it is characterized in that: the pH value of described reaction solution is 3～10.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304008A (en) * | 2013-07-10 | 2013-09-18 | 武汉大学 | Method for treating organic wastewater by using ferroferric oxide particle electrode in cooperation with electrochemical oxidization |
| CN103342405A (en) * | 2013-07-23 | 2013-10-09 | 哈尔滨工业大学 | Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate |
| CN103787486A (en) * | 2014-03-10 | 2014-05-14 | 武汉大学 | Organic-wastewater catalytic oxidation method |
| CN104496092A (en) * | 2014-12-30 | 2015-04-08 | 武汉大学 | Organic wastewater treatment method by recycling saturated activated carbon of adsorbing heavy metals |
| CN105731606A (en) * | 2016-03-24 | 2016-07-06 | 大连理工大学 | Method for treating organic wastewater through synergistic activation of persulfate using electrochemistry and Ni-Fe-LDH/rGO catalyst |
| CN107117776A (en) * | 2017-06-22 | 2017-09-01 | 哈尔滨理工大学 | A kind of peroxy-monosulfate that activates produces the method that free radical handles percolate |
| CN108117185A (en) * | 2016-11-30 | 2018-06-05 | 北京清源华建环境科技有限公司 | A kind of method for removing Organic Pollutants In Water |
| CN108452820A (en) * | 2018-02-09 | 2018-08-28 | 武汉大学 | A kind of carbonitride/α types ferric oxide catalyst, photoelectricity auxiliary Fenton-like and its application in treatment of Organic Wastewater |
| CN109437430A (en) * | 2018-11-16 | 2019-03-08 | 重庆大学 | A kind of method of thallium in advanced treatment of industrial wastewater |
| CN113620390A (en) * | 2021-06-30 | 2021-11-09 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Method for catalytically treating heavy metal-EDTA complex wastewater by using electrically-assisted Fe-MOF material |
| CN114044554A (en) * | 2021-10-08 | 2022-02-15 | 东北大学 | Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst |
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| CN102249378A (en) * | 2011-07-19 | 2011-11-23 | 武汉大学 | Method for treating organic waste water by using electrochemistry under assistance of persulfate |
| CN102500376A (en) * | 2011-10-24 | 2012-06-20 | 武汉大学 | Activated carbon loaded iron-cobalt oxide catalyst and application thereof in degrading organic pollutants |
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| KR20050120011A (en) * | 2004-06-17 | 2005-12-22 | 이동희 | Method and apparatus for treating high concentration organic wastewater using iron oxide powder |
| CN101973622A (en) * | 2010-10-19 | 2011-02-16 | 哈尔滨工业大学 | Method for accelerating monopersulfate and persulfate to produce free sulfate radicals |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304008A (en) * | 2013-07-10 | 2013-09-18 | 武汉大学 | Method for treating organic wastewater by using ferroferric oxide particle electrode in cooperation with electrochemical oxidization |
| CN103342405A (en) * | 2013-07-23 | 2013-10-09 | 哈尔滨工业大学 | Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate |
| CN103787486A (en) * | 2014-03-10 | 2014-05-14 | 武汉大学 | Organic-wastewater catalytic oxidation method |
| CN104496092A (en) * | 2014-12-30 | 2015-04-08 | 武汉大学 | Organic wastewater treatment method by recycling saturated activated carbon of adsorbing heavy metals |
| CN104496092B (en) * | 2014-12-30 | 2017-03-15 | 武汉大学 | The method for processing organic wastewater that a kind of heavy metal adsorption saturated activity charcoal is recycled |
| CN105731606A (en) * | 2016-03-24 | 2016-07-06 | 大连理工大学 | Method for treating organic wastewater through synergistic activation of persulfate using electrochemistry and Ni-Fe-LDH/rGO catalyst |
| CN108117185B (en) * | 2016-11-30 | 2020-09-25 | 北京清源华建环境科技有限公司 | Method for removing organic pollutants in water body |
| CN108117185A (en) * | 2016-11-30 | 2018-06-05 | 北京清源华建环境科技有限公司 | A kind of method for removing Organic Pollutants In Water |
| CN107117776A (en) * | 2017-06-22 | 2017-09-01 | 哈尔滨理工大学 | A kind of peroxy-monosulfate that activates produces the method that free radical handles percolate |
| CN108452820A (en) * | 2018-02-09 | 2018-08-28 | 武汉大学 | A kind of carbonitride/α types ferric oxide catalyst, photoelectricity auxiliary Fenton-like and its application in treatment of Organic Wastewater |
| CN109437430A (en) * | 2018-11-16 | 2019-03-08 | 重庆大学 | A kind of method of thallium in advanced treatment of industrial wastewater |
| CN113620390A (en) * | 2021-06-30 | 2021-11-09 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Method for catalytically treating heavy metal-EDTA complex wastewater by using electrically-assisted Fe-MOF material |
| CN114044554A (en) * | 2021-10-08 | 2022-02-15 | 东北大学 | Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst |
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Application publication date: 20130529 |