CN105251995B - A kind of preparation method of the nanometer nulvalent iron particle of spacetabs type - Google Patents
A kind of preparation method of the nanometer nulvalent iron particle of spacetabs type Download PDFInfo
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- CN105251995B CN105251995B CN201510750030.9A CN201510750030A CN105251995B CN 105251995 B CN105251995 B CN 105251995B CN 201510750030 A CN201510750030 A CN 201510750030A CN 105251995 B CN105251995 B CN 105251995B
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Abstract
A kind of preparation method of the nanometer nulvalent iron particle of green sustained release type, the material is using nanometer nulvalent iron particle as core, in Surface coating PASP；Using reducing process, in the PASP aqueous solution, Fe is reduced using reducing agents such as KBH4 or NaBH42+Obtain Fe0.The preparation method technique is simple, non-secondary pollution, and obtained nanometer nulvalent iron particle has preferably dispersiveness and reactivity, and it is for Cr6+, hexachloro-benzene removal effect be respectively higher than common iron powder 174% and more than 148%；It has good stability in atmosphere, can preserve the long period；And with good slow release, pollutant can long-term effectively be controlled, compared to common nano zero valence iron, acting duration improves more than 40%, with good market potential.
Description
Technical field
This patent is related to nano material preparation technology, especially a kind of preparation side of the nanometer nulvalent iron particle of spacetabs type
Method.
Background technology
Zero-valent Iron be it is a kind of be widely used in polluted underground water and the material of soil treatment, due to its have stronger electricity
Negativity and reproducibility, can be with multiple pollutant, and such as chlorobenzene class, heavy metal classes react, so as to reach depollution
The purpose of thing.Due to the unique nanoparticle structure of nano zero valence iron, it is set to possess specific surface area greatly, the features such as activity is strong,
With having faster reaction rate in above pollutant interaction process, treatment effect is far superior to common zeroth order iron powder,
With good market prospects.
The preparation method of current nano zero valence iron mainly has vapor phase method, liquid phase method and solid phase method.Nanometer prepared by vapor phase method
Zero-valent Iron has particle diameter small, the advantages of purity is high, but this method is higher to equipment requirement, operating difficulties；Solid phase method technique
It is fairly simple, but the nano zero valence iron poor dispersion prepared, easily reunite.Being most widely used for liquid phase method, can
The nano zero valence iron of good dispersion property is made, but not yet solves nano zero valence iron and uses preceding aerial stability problem；
Simultaneously as underground water and pollutant in soil absorption discharge more slow, substantial amounts of nano zero valence iron on soil particle surface
Disposable release causes the waste of material and unendurable contaminated site is controlled.In the first research of this patent,
Use the natural high molecular substances such as chitosan, guar gum to coat nano zero-valence iron surface, solved material and exist
Stability problem in air, it is to avoid the secondary pollution of covering material；But the problem of not yet solving nano zero valence iron slow release,
And due to the limitation of its degree of polymerization of natural high molecular substance, cause the nanocomposite applications field more single.
This patent carries out the synthesis of nano zero valence iron in poly-aspartic-acid (PASP) solution, can prepare particle compared with
It is small, it is distributed more uniform particle；And due to coating functions of the PASP for nanometer nulvalent iron particle surface, can be obviously improved
Its aerial stability.PASP is that a kind of water-soluble amino acids are birdsed of the same feather flock together compound, and environment compatibility is high, decomposition in the environment
Do not produce secondary pollution；In water with can slowly be decomposed in soil, its nano zero valence iron coated can be slowly discharged into
In contaminated site, to the target compound in the control environment of continuous and effective；And the PASP is artificial synthesized, and its degree of polymerization can
Control, the PASP degree of polymerization can be regulated and controled according to the type, content and release rule of pollutant and then regulates and controls Zero-valent Iron in the environment
Rate of release, realize environmental contaminants release with Zero-valent Iron release it is harmonious.Utilize PASP reduction method for preparing nanometer zero
Valency iron at home and abroad has not been reported, and the present invention is as starting point, it is proposed that a kind of nanometer nulvalent iron particle of spacetabs type
Preparation method.
The content of the invention
It is an object of the invention to improve the application effect of nano zero valence iron in the environment, there is provided a kind of nanometer of spacetabs type
The preparation method of nulvalent iron particle, the preparation technology is simple, non-secondary pollution, and obtained nanometer nulvalent iron particle has preferably
Stability, spacetabs type, dispersiveness and reactivity.
Technical scheme：
A kind of preparation method of the nanometer nulvalent iron particle of spacetabs type, the material using nanometer nulvalent iron particle as core,
Surface coating PASP, its specific preparation process is as follows：
(1) molecular weight is added in pure water for 15000~20000 PASP gels, heating makes it fully dissolve, added
Pure water carries out constant volume, obtains the PASP solution that mass fraction is 0.01~0.1%；
(2) 0.5g or so FeSO is weighed4·7H2O is added in the 40~60mL PASP solution, and mechanical agitation makes
It is sufficiently mixed, and nitrogen is passed through in mixed process, is removed the dissolved oxygen in solution, is obtained ferrous sulfate/PASP mixed solution；
(3) 0.4g or so NaBH is weighed4Or KBH4In powder, the mixed solution for being added to the ferrous sulfate/PASP,
The NaOH solution that 2mL concentration is 0.5mol/L is added dropwise, mechanical agitation is sufficiently mixed it, obtains nano zero-valence ferrous solution；
(4) the nano zero-valence ferrous solution is stood on kicker magnet, accelerates it to precipitate by magneticaction, use distillation
Water washing more than twice, powder is dried in vacuum drying chamber, nanometer nulvalent iron particle is obtained.
It is preferred that, during described preparation PASP solution, prepared using anaerobic water, it is preferred that using ultrapure
Water is prepared.
It is preferred that, during the hungry mixed solution for preparing ferrous sulfate/PASP, it is passed through nitrogen more than 2 hours.
It is preferred that, described prepares in nano zero valence iron solution processes, mechanical agitation 10min~50min, it is preferred that
20min~40min.
It is preferred that, in described process of vacuum drying, pressure is below 100pa, below 50pa preferably；Drying time
More than 30min, more than 45min preferably.
The advantage of the invention is that：This patent preparation technology is simple, non-secondary pollution, and scale industrial production can be achieved；
Nanometer nulvalent iron particle made from this patent has preferably dispersiveness and reactivity, and its using effect is far above common iron
Powder；It has good stability in atmosphere, can preserve the long period；And with good slow release, can be to pollution
Thing is controlled long-term effectively, with good market potential.
Brief description of the drawings
The scanning electron microscope (SEM) photograph for the nanometer nulvalent iron particle that Fig. 1 is prepared for the present invention
Fig. 2 removes Cr in water removal for nanometer nulvalent iron particle prepared by the present invention with common iron powder, common nano zero valence iron6+'s
Effect contrast figure
Fig. 3 removes chlordene in water removal for nanometer nulvalent iron particle prepared by the present invention with common iron powder, common nano zero valence iron
The effect contrast figure of benzene
Embodiment
Specific examples below has carried out further detailed description to present disclosure, is only the specific reality of the present invention
Example is applied, is not intended to limit the invention.
Embodiment 1：
A kind of preparation method of the nanometer nulvalent iron particle of spacetabs type, the material using nanometer nulvalent iron particle as core,
Surface coating PASP, its specific preparation process is as follows：Molecular weight is added in deionized water for 20000 PASP particles, plus
Heat makes it fully dissolve, and adds deionized water and carries out constant volume, obtains the PASP solution that mass fraction is 0.1%；Weigh 0.5g's
FeSO4·7H2O is added in the 50mL PASP solution, and mechanical agitation is sufficiently mixed it, and nitrogen is passed through in mixed process,
The dissolved oxygen in solution is removed, ferrous sulfate/PASP mixed solution is obtained；Weigh 0.4g NaBH4Powder, is added to described
In ferrous sulfate/PASP mixed solution, the NaOH solution that 2mL concentration is 0.5mol/L is added dropwise, mechanical agitation makes it fully mix
Merge reaction 30min, obtain nano zero-valence ferrous solution；The nano zero-valence ferrous solution is stood on kicker magnet, passes through magnetic force
Effect accelerates its precipitation, and the above is washed twice using distilled water, and powder is done in pressure is 30pa vacuum drying chamber
Dry 30min, obtains nanometer nulvalent iron particle；(such as Fig. 1) is scanned to the nanometer nulvalent iron particle using ESEM, can
Observe that the particle of the material is evenly distributed, and the uniform PASP coatings of particle surface can be clearly apparent.
Embodiment 2：
Nanometer nulvalent iron particle prepared by the present invention carries out Cr6+Clearance experiment.This patent described in 0.5g is taken to prepare
Nano zero valence iron be added to 100mL Cr6+Concentration for 100mg/L simulation faintly acid heavy metal polluted waste water in, put
Reacted in the constant temperature oscillation case for entering 25 DEG C, sampling at regular intervals uses Cr in ion electrode measurement water body6+Concentration, is obtained
To the Cr of the material6+Remove curve.
Embodiment 3：
Nanometer nulvalent iron particle prepared by the present invention carries out the clearance experiment of chlorobenzene class.Take this patent described in 0.05g
The nano zero valence iron of preparation is added in the simulation faintly acid chloro- benzenes contamination waste water that 150mL chlordene benzene concentration is 200 μ g/L,
Reacted in the constant temperature oscillation case for putting it into 25 DEG C, sample, sample is extracted at regular intervals using n-hexane
Chlordene benzene concentration in gas chromatographic measurement sample is used afterwards, and the hexachloro-benzene for obtaining the material removes curve.
Comparative example 1：
Nano zero valence iron prepared by this patent is replaced with common nano zero valence iron, and other steps repeat embodiment respectively
2、3。
Comparative example 2：
Nano zero valence iron prepared by this patent is replaced with common zeroth order iron powder, other steps repeat respectively embodiment 2,
3。
As shown in Fig. 2 nanometer nulvalent iron particle prepared by the present invention, it is for Cr6+Removal effect be higher than common iron powder
More than 174%；Compared to common nano zero valence iron, acting duration improves more than 40%.As shown in figure 3, prepared by the present invention
Nanometer nulvalent iron particle, its for hexachloro-benzene removal effect be higher than common iron powder more than 148%；Compared to common nanometer zero
Valency iron, acting duration improves more than 60%.
Claims (5)
1. a kind of preparation method of the nanometer nulvalent iron particle of green sustained release type, it is characterised in that：The nanometer nulvalent iron particle with
Nanometer nulvalent iron particle is core, and in Surface coating PASP, its specific preparation process is as follows：It is 5000~15000 by molecular weight
PASP particles be added in pure water, heating makes it fully dissolve, and adds pure water and carries out constant volume, obtain mass fraction for 0.01~
0.1% PASP solution；Weigh 0.5g or so FeSO4·7H2O is added in the 40~60mL PASP solution, and machinery is stirred
Mixing is sufficiently mixed it, and nitrogen is passed through in mixed process, removes the dissolved oxygen in solution, obtains ferrous sulfate/PASP mixing
Solution；Weigh 0.4g or so NaBH4Or KBH4In powder, the mixed solution for being added to the ferrous sulfate/PASP, 2mL is added dropwise
Concentration is 0.5mol/L NaOH solution, and mechanical agitation is sufficiently mixed it, obtains nano zero-valence ferrous solution；By the nanometer zero
Valency ferrous solution is stood on kicker magnet, accelerates it to precipitate by magneticaction, and the above is washed twice using distilled water, and powder is existed
It is dried in vacuum drying chamber, obtains nanometer nulvalent iron particle.
2. a kind of preparation method of the nanometer nulvalent iron particle of green sustained release type according to claim 1, it is characterised in that
During preparing PASP solution, prepared using anaerobic water.
3. a kind of preparation method of the nanometer nulvalent iron particle of green sustained release type according to claim 1, it is characterised in that
During the mixed solution for preparing ferrous sulfate/PASP, nitrogen is passed through more than 2 hours.
4. a kind of preparation method of the nanometer nulvalent iron particle of green sustained release type according to claim 1, it is characterised in that
Prepare in nano zero valence iron solution processes, mechanical agitation 10min~50min.
5. a kind of preparation method of the nanometer nulvalent iron particle of green sustained release type according to claim 1, it is characterised in that
In process of vacuum drying, pressure is below 100pa, more than drying time 30min.
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| CN105802631B (en) * | 2016-04-29 | 2020-10-02 | 航天凯天环保科技股份有限公司 | Transition state iron-based heavy metal immobilized reagent and preparation method thereof |
| CN106077624B (en) * | 2016-07-26 | 2019-01-04 | 昆明理工大学 | A kind of micelle modified modified Nano nulvalent iron particle and its preparation method and application |
| CN107082479B (en) * | 2017-06-02 | 2021-06-15 | 北京大学 | Iron-based dephosphorization flocculant with slow release function and preparation method and application thereof |
| CN107350469B (en) * | 2017-06-27 | 2019-06-18 | 东南大学 | A kind of dispersing method of Zero-valent Iron |
| CN109796986A (en) * | 2019-01-28 | 2019-05-24 | 葛畅 | A kind of preparation method of the soil remediation medicament for valence heavy metal ions |
| CN112846214A (en) * | 2019-11-27 | 2021-05-28 | 北京化工大学 | Method for green synthesis of slow-release nano zero-valent iron by using gleditsia sinensis lam extract and application |
| CN113231104B (en) * | 2021-05-31 | 2022-06-14 | 华中科技大学 | Amino acid modified nano zero-valent iron material and preparation method thereof |
| CN113275037B (en) * | 2021-05-31 | 2022-11-11 | 华中科技大学 | Method for treating organic solvent by heterogeneous Fenton-like method |
| CN114247475A (en) * | 2021-12-21 | 2022-03-29 | 大连理工大学 | Preparation method and application of polyaspartic acid and sodium hydrosulfite composite modified nano zero-valent iron material |
| CN114751502B (en) * | 2022-03-24 | 2023-06-23 | 陕西省中勘环境地质研究中心有限公司 | Core-shell structure modified nano zero-valent iron and preparation method and application thereof |
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Effective date of registration: 20210907 Address after: 518033 703a8, building a, Xinghe century, No. 3069, CaiTian Road, Gangxia community, Futian street, Futian District, Shenzhen, Guangdong Patentee after: Shenzhen carbon star Water Technology Co.,Ltd. Patentee after: Carbon Star Technology (Shenzhen) Group Co.,Ltd. Address before: 100088 Floor 1, Building 52, 44 North Third Ring Road, Haidian District, Beijing Patentee before: ZENITY ENVIRONMENT (BEIJING) Co.,Ltd. |
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