CN103332766A - Water and waste water purification method for improving reactivity of zero-valent iron through magnetic field pretreatment - Google Patents
Water and waste water purification method for improving reactivity of zero-valent iron through magnetic field pretreatment Download PDFInfo
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- CN103332766A CN103332766A CN2013102435889A CN201310243588A CN103332766A CN 103332766 A CN103332766 A CN 103332766A CN 2013102435889 A CN2013102435889 A CN 2013102435889A CN 201310243588 A CN201310243588 A CN 201310243588A CN 103332766 A CN103332766 A CN 103332766A
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Abstract
The invention belongs to the technical field of water and waste water treatment, and relates to a water and waste water purification method for improving reactivity of zero-valent iron through magnetic field pretreatment. The method is characterized by pretreating the zero-valent iron by utilizing the magnetic field, and adding the pretreated zero-valent iron into a relevant reactor for purifying the water or waste water. The method aims at the application of the zero-valent iron in environment pollution improvement. The zero-valent iron is pretreated in the magnetic field, and a passive film on the surface of the zero-valent iron is destroyed, so that the corrosion rate of the zero-valent iron can be accelerated, and the removal rate of the contaminant can be improved. The method can be used not only for improving the reactivity of unused zero-valent iron but also for improving the reactivity of used zero-valent iron with the passive film on the surface. Compared with the prior art, the method is simple to use, does not consume any chemical substance, and is environment-friendly and energy-saving, after the reaction, no toxic metal ions are left, and the method has no ecotoxicity.
Description
Technical field
The invention belongs to water and technical field of waste water processing, relate to water and purification method for effluent that the pre-treatment of a kind of magnetic field improves the Zero-valent Iron reactive behavior.
Background technology
Zero-valent Iron is inexpensive, environmental friendliness and be widely used in the removal of environmental pollutant.Corrosion reaction, i.e. oxygenant (O in Zero-valent Iron and the water easily take place in Zero-valent Iron in water
2, H
+Or H
2O) electrochemical reaction takes place, anodic reaction is converted into deliquescent Fe for the iron betatopic
2+Or insoluble ironic hydroxide, the cathodic reaction of following is reduction reaction.In the corrosion process of Zero-valent Iron, can produce Fe
2+ (aq), Fe
3+ (aq), H
2And various throw outs such as Fe (OH)
2, Fe (OH)
3, Fe
3O
4, Fe
2O
3, corrosion product such as FeOOH, patina.These corrosion reactions and corrosion product make Zero-valent Iron remove pollutent in the water by effect such as reduction, absorption, coagulation just, and the erosion rate of Zero-valent Iron in water directly influenced the speed of reaction of itself and pollutent.Early 1970s occurs can reducing the patent of removing chlorinatedorganic in the aqueous solution about Zero-valent Iron, the eighties in 20th century, Senzaki etc. proposed to remove organic pollutant in the water with Zero-valent Iron, and Gillham etc. proposes Zero-valent Iron and is used for contaminated phreatic original position reparation subsequently.Zero-valent Iron has been widely used in degrading and has removed organic or inorganic pollutent in the environment in recent years, comprises various chlorinatedorganics, heavy metal (Cr (VI), As (V), As (III), Cu
2+, Pb
2+Deng), azoic dyestuff, nitryl aromatic family, nitrate, perchlorate etc.
Reaction between Zero-valent Iron and the pollutent or consume hydrogen ion or produce hydroxide radical causes that the pH value of solution value raises rapidly in the reaction process, and (hydrogen) oxide compound that generates various iron is covered in the Zero-valent Iron surface and forms passive film.Under strong acidic condition, the H in the solution
+Can prevent sedimental generation, make Zero-valent Iron keep unsalted surface to continue and pollutant reaction.Under slightly acidic or neutrallty condition, the porosity of initial reaction stage passive film is higher, and is less to the influence of the speed of reaction between Zero-valent Iron and the pollutent, and along with the carrying out of reaction, passivation film thickness increases and porosity reduces, and can seriously reduce Zero-valent Iron and H
2O/O
2Or and pollutent between corrosion reaction, thereby reduce the removal speed of pollutent.Therefore the depollution ability of Zero-valent Iron reduces gradually along with the rising of pH and the prolongation in reaction times, and reaction process can accumulate more unmanageable intermediate product sometimes, the reduction reaction rate of many materials is difficult to reach the requirement of large-scale application.
Be to improve the reactive behavior of Zero-valent Iron, method commonly used has two kinds, and the one, at iron surface mix another kind of metal and its formation bimetal, the 2nd, the particle diameter by the reduction Zero-valent Iron is prepared into nanometer iron with it.The bimetal system of appearing in the newspapers at present comprises Au/Fe, Pt/Fe, Co/Fe, Cu/Fe, Ni/Fe, Pd/Fe, Ag/Fe etc., another kind of metal price height outside the deironing, toxicity are big, and bimetallic reactivity ratio's Zero-valent Iron improves limited even be lower than simple Zero-valent Iron, thereby have limited its application.Nanometer abrasive grit footpath is little, specific surface area is big, with the reaction of other heavy metal contaminants in have high reaction activity and high, but nanometer iron price than common iron powder high a lot, easily reunite, easily lose activity, vigorous reaction between nanometer iron and the water causes some nanometer iron only can bring into play the effect of removal pollutent, and the toxicity problem of nano material is a focus of paying close attention at present, and these problems have all limited the application of nanometer iron.Therefore must seek other more economically, practicality, safe method improve the speed of reaction of Zero-valent Iron and pollutent, expands its suitable pH scope.
Summary of the invention
The objective of the invention is to the defective for the two kinds of common methods (preparation bimetal or nanometer iron) that overcome existing raising Zero-valent Iron reactive behavior, and provide the pre-treatment of a kind of magnetic field to improve the method for Zero-valent Iron reactive behavior.
For achieving the above object, the present invention is by the following technical solutions:
The pre-treatment of a kind of magnetic field improves water and the purification method for effluent of Zero-valent Iron reactive behavior, it is characterized in that this method may further comprise the steps:
(1) utilize magnetic field that Zero-valent Iron is carried out pre-treatment;
(2) adding in the corresponding reactor through pretreated Zero-valent Iron, water or waste water are purified.
In the described step (1), the pretreated time of magnetic field was advisable with 3-8 minute.
In the described step (1), magnetic field is stationary magnetic field, alternating magnetic field, pulsating magnetic field or pulsed magnetic field.
In the described step (1), the intensity of low-intensity magnetic field is advisable with 30-70 mT.
In the described step (1), Zero-valent Iron can be that original Zero-valent Iron also can be that there is the Zero-valent Iron of passive film on used, surface.
Described step (2) can be to utilize the reducing power of Zero-valent Iron or adsorptive power to remove each heavy metal species and organic pollutant in water and the waste water, also can be to utilize the catalytic capability of Zero-valent Iron to activate persulphate or hydrogen peroxide is removed various organic pollutants.
Reactor in the described step (2) can be that complete mixing reactor also can be fixed-bed reactor.
The present invention is primarily aimed at the application and development of Zero-valent Iron in environmental pollution improvement.Ultimate principle of the present invention be by in magnetic field (30 ~ 70 mT) Zero-valent Iron is carried out pre-treatment, destroy the ironing surface passive film of zeroth order, thereby can accelerate the erosion rate of Zero-valent Iron, and then improve the removal speed of pollutent.The reactive behavior that present method is not only applicable to original Zero-valent Iron still improves, and also can be applicable to the raising that there is the Zero-valent Iron reactive behavior of passive film on used, surface.Compare with the method for existing raising Zero-valent Iron reactive behavior, use simply, do not consume any chemical substance, green energy conservation; The no toxic metal ion residues in reaction back is without any eco-toxicity.
Description of drawings
Fig. 1 is in the embodiment of the invention 1, at pH=6.0, and Se (IV) starting point concentration 5.0 mg/L, Zero-valent Iron concentration 1.0 g/L, the magnetic field pre-treatment removes Se (IV) effect of kinetics to Zero-valent Iron.Among the figure-▼-expression is through the removal kinetic curve of the pretreated Zero-valent Iron in magnetic field to Se (IV) ,-●-expression is through the removal kinetic curve of the pretreated Zero-valent Iron in magnetic field to Se (IV).
Embodiment
Further specify the present invention below in conjunction with embodiment and accompanying drawing.
Embodiment 1
A kind of magnetic field pre-treatment in the present embodiment improves the method for Zero-valent Iron reactive behavior, may further comprise the steps:
(1) Zero-valent Iron is carried out pre-treatment in magnetic field, used magnetic field is alternating magnetic field, and the magnetic field maximum strength is about 30 mT, and frequency is about 0.01 Hz, and pretreatment time is 5 minutes;
(2) respectively containing in Se (IV) solution through the pretreated Zero-valent Iron in magnetic field and untreated Zero-valent Iron adding, reactor adopts hybrid fully, and the starting point concentration of Se (IV) is 5.0 mg/L, pH=6.0, Zero-valent Iron concentration 1.0 g/L.The results are shown in Figure 1.As seen from Figure 1, the magnetic field pre-treatment can improve the speed of reaction of Zero-valent Iron and Se (IV) greatly, shortens the reaction times.Through can all removing Se (IV) in the pretreated Zero-valent Iron in magnetic field 60 minutes, but can only remove 58% Se (IV) in 240 minutes without the pretreated Zero-valent Iron in magnetic field.
Embodiment 2
A kind of magnetic field pre-treatment in the present embodiment improves the method for Zero-valent Iron reactive behavior, may further comprise the steps:
(1) Zero-valent Iron is carried out pre-treatment in magnetic field, used magnetic field is the stationary magnetic field, and magneticstrength is about 70 mT, and pretreatment time is 3 minutes;
(2) respectively containing in Cr (VI) solution through the pretreated Zero-valent Iron in magnetic field and untreated Zero-valent Iron adding, reactor adopts hybrid fully, and the starting point concentration of Cr (VI) is 5.0 mg/L, pH=5.0, Zero-valent Iron concentration 0.5 g/L.The magnetic field pre-treatment can improve the speed of reaction of Zero-valent Iron and Cr (VI) greatly, shortens the reaction times.Through can all removing Cr (VI) in the pretreated Zero-valent Iron in magnetic field 70 minutes, but can only remove 98% Cr (VI) in 180 minutes without the pretreated Zero-valent Iron in magnetic field.
Embodiment 3
A kind of magnetic field pre-treatment in the present embodiment improves the method for Zero-valent Iron reactive behavior, may further comprise the steps:
(1) Zero-valent Iron is carried out pre-treatment in magnetic field, used magnetic field is pulsed magnetic field, the about 0-50 mT of magneticstrength, and frequency is about 1 Hz, and pretreatment time is 8 minutes;
(2) respectively containing in Se (VI) solution through the pretreated Zero-valent Iron in magnetic field and untreated Zero-valent Iron adding, reactor adopts hybrid fully, and the starting point concentration of Se (VI) is 40.0 mg/L, pH=6.0, Zero-valent Iron concentration 1.0 g/L.The magnetic field pre-treatment can improve the speed of reaction of Zero-valent Iron and Se (VI) greatly, shortens the reaction times.95% Se (VI) can be removed through the pretreated Zero-valent Iron in magnetic field in 90 minutes, but 20% Se (VI) can only be removed in 1440 minutes without the pretreated Zero-valent Iron in magnetic field.
Embodiment 4
A kind of magnetic field pre-treatment in the present embodiment improves the method for Zero-valent Iron reactive behavior, may further comprise the steps:
(1) Zero-valent Iron is carried out pre-treatment in magnetic field, used magnetic field is pulsating magnetic field, and magneticstrength is about 20-40 mT, and frequency is about 0.01 Hz, and pretreatment time is 8 minutes;
(2) in complete, dyeing waste water Methylene blue starting point concentration 50 mg/L, regulating initial pH value is 4.0, adds the hydrogen peroxide of 170 mg/L in the above-mentioned dyeing waste water earlier, the Zero-valent Iron that adds 100 mg/L again starts reaction.When using through the pretreated Zero-valent Iron in magnetic field, the clearance of methylene blue can reach 100% in 20 min; When using without the pretreated Zero-valent Iron in magnetic field, removing methylene blue fully needs 90 min.As seen the magnetic field pre-treatment can improve speed of reaction greatly, shortens the reaction times.
Embodiment 5
A kind of magnetic field pre-treatment in the present embodiment improves the method for Zero-valent Iron reactive behavior, may further comprise the steps:
(1) Zero-valent Iron is carried out pre-treatment in magnetic field, used magnetic field is the stationary magnetic field, and magneticstrength is about 40 mT, and pretreatment time is 4 minutes;
(2) in fixed-bed reactor, the starting point concentration of dyeing waste water gold orange G is 91 mg/L, and regulating initial pH value is 3.0, adds the Sodium Persulfate of 476 mg/L in the above-mentioned dyeing waste water earlier, and the Zero-valent Iron that adds 112 mg/L again starts reaction.When using through the pretreated Zero-valent Iron in magnetic field, the clearance of gold orange G can reach 96% in 16 min; When using without the pretreated Zero-valent Iron in magnetic field, the clearance of gold orange G reaches 95% needs 100 min.
Embodiment 6
A kind of magnetic field pre-treatment in the present embodiment improves the method for Zero-valent Iron reactive behavior, may further comprise the steps:
(1) carry out pre-treatment after the Zero-valent Iron washing lyophilize of wearing out 48 hours in magnetic field in water, used magnetic field is alternating magnetic field, and the magnetic field maximum strength is about 30 mT, and frequency is about 0.01 Hz, and pretreatment time is 7 minutes;
(2) contain in Se (IV) solution joining through the pretreated Zero-valent Iron in magnetic field and untreated Zero-valent Iron respectively, reactor adopts hybrid fully, and the starting point concentration of Se (IV) is 40.0 mg/L, pH=6.0, Zero-valent Iron concentration 1.0 g/L.The speed of reaction that the magnetic field pre-treatment can improve aging Zero-valent Iron and Se (IV) greatly shortens the reaction times.96% Se (IV) can be removed through the pretreated Zero-valent Iron in magnetic field in 45 minutes, but 41% Se (IV) can only be removed in 300 minutes without the pretreated Zero-valent Iron in magnetic field.
Claims (1)
1. a magnetic field pre-treatment improves water and the purification method for effluent of Zero-valent Iron reactive behavior, it is characterized in that this method may further comprise the steps:
(1) utilize magnetic field that Zero-valent Iron is carried out pre-treatment;
(2) adding in the reactor through pretreated Zero-valent Iron, water or waste water are purified.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944566A (en) * | 2015-07-02 | 2015-09-30 | 南开大学 | Method for increasing chlorine organic waste water dechlorination rate through pre-magnetization Fe0/peroxysulphate system |
| CN105060454A (en) * | 2015-07-02 | 2015-11-18 | 华北电力大学 | Method for removing pollutants in water through magnetic field reinforced Hangjin 2# clay supported nanometer zero-valent iron |
| CN105859015A (en) * | 2016-05-27 | 2016-08-17 | 山东大学 | Method for removing orange yellow I in printing and dyeing wastewater by using sulfurized modified zero-valent iron material under effect of low-intensity magnetic field |
| CN106565010A (en) * | 2016-10-18 | 2017-04-19 | 哈尔滨工业大学 | Method for treating organic pollutants in water |
| CN106630045A (en) * | 2016-12-23 | 2017-05-10 | 绍兴文理学院 | Method for fast degrading dyestuff waste water under condition of low iron feeding quantity |
| CN107188291A (en) * | 2017-06-05 | 2017-09-22 | 华中师范大学 | A kind of liquid nitrogen cryogenics processing business iron powder strengthens the method that its reduction removes pollutant ability |
| CN108264133A (en) * | 2017-12-29 | 2018-07-10 | 海天水务集团股份公司 | A kind of Zero-valent Iron-passivated iron micro-electrolysis stuffing and preparation method thereof |
| CN109570219A (en) * | 2018-11-12 | 2019-04-05 | 同济大学 | Heavy metal-polluted soil restorative procedure based on modified Zero-valent Iron |
| CN110104742A (en) * | 2019-04-02 | 2019-08-09 | 山东大学 | A kind of method and separate type continuous flow reactor of combination aging magnetization pretreatment Zero-valent Iron removal Cr (VI) |
| CN112142181A (en) * | 2020-08-10 | 2020-12-29 | 南开大学 | Method for treating antibiotics in water by pre-magnetizing zero-valent iron/chelating agent system |
| CN113415917A (en) * | 2021-06-22 | 2021-09-21 | 同济大学 | Zero-valent iron wastewater treatment system and treatment method coupled with surface updating device |
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| CN102060368A (en) * | 2010-11-24 | 2011-05-18 | 南京大学 | Method for improving utilization rate of zero-valent iron in zero-valent iron pretreatment of chemical wastewater |
| CN102807272A (en) * | 2012-09-01 | 2012-12-05 | 同济大学 | Method for removing Se(IV)/Se(VI) from water by magnetic field enhanced zero-valent iron |
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Cited By (14)
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|---|---|---|---|---|
| CN105060454B (en) * | 2015-07-02 | 2018-01-16 | 华北电力大学 | A kind of method that magnetic field-intensification Hanggin 2# soil load nano zero valence iron removes water pollutant |
| CN105060454A (en) * | 2015-07-02 | 2015-11-18 | 华北电力大学 | Method for removing pollutants in water through magnetic field reinforced Hangjin 2# clay supported nanometer zero-valent iron |
| CN104944566A (en) * | 2015-07-02 | 2015-09-30 | 南开大学 | Method for increasing chlorine organic waste water dechlorination rate through pre-magnetization Fe0/peroxysulphate system |
| CN105859015A (en) * | 2016-05-27 | 2016-08-17 | 山东大学 | Method for removing orange yellow I in printing and dyeing wastewater by using sulfurized modified zero-valent iron material under effect of low-intensity magnetic field |
| CN106565010A (en) * | 2016-10-18 | 2017-04-19 | 哈尔滨工业大学 | Method for treating organic pollutants in water |
| CN106630045A (en) * | 2016-12-23 | 2017-05-10 | 绍兴文理学院 | Method for fast degrading dyestuff waste water under condition of low iron feeding quantity |
| CN107188291A (en) * | 2017-06-05 | 2017-09-22 | 华中师范大学 | A kind of liquid nitrogen cryogenics processing business iron powder strengthens the method that its reduction removes pollutant ability |
| CN107188291B (en) * | 2017-06-05 | 2020-08-04 | 华中师范大学 | Method for enhancing pollutant reduction removal capability of commercial iron powder through liquid nitrogen low-temperature treatment |
| CN108264133A (en) * | 2017-12-29 | 2018-07-10 | 海天水务集团股份公司 | A kind of Zero-valent Iron-passivated iron micro-electrolysis stuffing and preparation method thereof |
| CN109570219A (en) * | 2018-11-12 | 2019-04-05 | 同济大学 | Heavy metal-polluted soil restorative procedure based on modified Zero-valent Iron |
| CN110104742A (en) * | 2019-04-02 | 2019-08-09 | 山东大学 | A kind of method and separate type continuous flow reactor of combination aging magnetization pretreatment Zero-valent Iron removal Cr (VI) |
| CN112142181A (en) * | 2020-08-10 | 2020-12-29 | 南开大学 | Method for treating antibiotics in water by pre-magnetizing zero-valent iron/chelating agent system |
| CN113415917A (en) * | 2021-06-22 | 2021-09-21 | 同济大学 | Zero-valent iron wastewater treatment system and treatment method coupled with surface updating device |
| CN113415917B (en) * | 2021-06-22 | 2022-11-18 | 同济大学 | Zero-valent iron wastewater treatment system and treatment method coupled with surface updating device |
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Application publication date: 20131002 |