CN104759635B - A kind of preparation method of loaded nano zero-valent iron composite material - Google Patents
A kind of preparation method of loaded nano zero-valent iron composite material Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of loaded nano zero-valent iron composite material, comprise the steps: a) to prepare micro-/receive compound flower-shaped self-supporting Mg (OH)2Microsphere；B) distribute it in finite concentration ferrum/ferrous ions soln；C) dripping sodium borohydride solution to b) mixed solution, in-situ reducing ferrum/ferrous ion prepares Mg (OH)2The nano zero valence iron of load.It is an advantage of the current invention that: 1. volume production is easy in preparation method mild condition, simple to operate, environmental protection；2. raw material sources are extensive, cheap, are beneficial to reduce cost；3. the load capacity of loaded nano Zero-valent Iron is adjustable, uniform product appearance, and size is controlled；4. the environmental contaminants such as nano zero-valence iron composite material heavy metal ion, organic solution and the dyestuff obtained by the present invention have efficient removal ability, can be as water treatment agent for environmental area.
Description
Technical field
The present invention relates to the preparation method of a kind of loaded nano zero-valent iron composite material, belong to inorganic nano material
Material field.
Background technology
Nano zero valence iron (nZVI), owing to having the advantages such as high-ratio surface, high activity, strong reducing property, successfully should
For processing chloro organic cpd, nitroaromatic, dyestuff and heavy metal pollution in subsoil water/waste water
Thing.Subsoil water in-situ immobilization place based on nZVI material in the whole world more than 20.But, nZVI
Small particle and the reunion that causes of self the magnetic activity, life-span and the treatment effeciency that are caused drastically decline, seriously
Hinder nZVI large-scale application.By nZVI is supported on other materials, can effectively solve above-mentioned
Problem, the backing material reported includes two classes: a class is natural minerals, as kieselguhr, bentonite,
Kaolinite, column clay etc.；Another kind of is synthetic material, such as chelating resin, mesoporous carbon, titanium dioxide
Silicon, Graphene etc..Above-mentioned backing material can effectively disperse nZVI granule to a certain extent, but has in them
Preparation method complicated, condition is harsh, expensive, it is impossible to large-scale application；Natural minerals is drawn materials
Extensively, low price, but after load, pattern is uneven, it is impossible to play the maximal efficiency of nZVI.Traditional support material
Expect the often physics of Special attention will be given to material, chemical stability and mechanical strength, formed with nano zero valence iron
Composite typically only serves the effect of single carrier, for improving the dispersibility of nano zero valence iron granule,
Reduce it to reunite.If backing material is while realizing its " carrier " function, itself there is removal water pollutant
Ability, and the realization of nano zero valence iron function can be promoted, will greatly strengthen the availability of nano zero valence iron,
Promote the popularization that it is applied.
Nanometer Mg (OH)2As water treatment agent a kind of low cost, eco-friendly originally at acid waste water
The aspects such as reason, heavy metal removing, decolorizing printing and dyeing waste water show good application prospect, but it is to pollutant
Removal be confined to physical absorption and precipitation, limited to obstinate Organic substance and metal ion effect.Chemistry
The Mg (OH) of sedimentation method synthesis2Usually easily formed the flower-like structure of self-supporting by regulation and control, thus have greatly than
Surface area and the potential good load capacity to nZVI.NZVI and Mg (OH)2Two kinds of environmental treatment materials
The combination of material is expected to the advantage of integrated two materials, constructs out a kind of with low cost, reduces nZVI and reunite, thus
Water pollutant is had the system of efficient removal ability.
Summary of the invention
It is an object of the invention to provide a kind of method that liquid phase reduction prepares loaded nano Zero-valent Iron, should
The features such as method has that preparation process is simple, mild condition, with low cost, green non-poisonous.
For achieving the above object, the technical solution used in the present invention is as follows:
The preparation method of a kind of loaded nano Zero-valent Iron complex with High-efficient Water process performance, including such as
Lower step:
A) prepare micro-/receive compound flower-shaped self-supporting Mg (OH)2Microsphere；
B) the water-ethanol mixed solution of ferrum/ferrous ion is prepared；
C) sodium borohydride solution is prepared；
D) by the Mg (OH) of preparation in step a)2Microsphere joins prepares ferrum/ferrous ions soln in step b)
In, ultrasonic making is uniformly dispersed, and obtains disperseing Mg (OH)2Ferrum/ferrous ions soln；
E) d that the sodium borohydride solution obtained in step c) is added drop-wise to certain speed) mixing prepared of step
In solution, in-situ reducing ferrum/ferrous ion prepares Mg (OH)2The nano zero valence iron of load.
F) being separated by solid-liquid suspension e) obtained, the black solid of collection is product.
Preferably, described source of iron is FeSO4·7H2O, ferrous ion concentration is 0.05mol/L.
Preferably, the concentration of described sodium borohydride aqueous solution is 0.25mol/L.
Preferably, described nano zero valence iron load capacity is 50%.
Preferably, described sodium borohydride aqueous solution drop rate is 3mL/min.
Preferably, described preparation process stir speed (S.S.) is 300r/min.
It is an advantage of the current invention that:
1. utilize method disclosed by the invention to have mild condition, operation letter to prepare loaded nano Zero-valent Iron
Feature single, that volume production is easy in environmental protection；
2. the raw material sources that the present invention is utilized are extensive, cheap, are beneficial to reduce cost；
3. the load capacity of loaded nano Zero-valent Iron is adjustable, uniform product appearance, and size is controlled；
4. nano zero-valence iron composite material heavy metal ion, organic solution and the dyestuff obtained by the present invention
Deng environmental contaminants, there is efficient removal ability, can be as water treatment agent for environmental area.
Accompanying drawing explanation
Fig. 1 embodiment of the present invention 1 obtain micro-/receive compound flower-shaped self-supporting Mg (OH)2The scanning electron of microsphere
Microphotograph, a) and b) is respectively the electron scanning micrograph under different amplification；
Fig. 2 is the Mg (OH) of preparation in embodiment 12Support nano zero-valence iron composite material photo, a) and
B) it is respectively the photo under different amplification.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are only used for
The bright present invention rather than restriction the scope of the present invention.
Embodiment 1
Under step one, room temperature, 1mol/L NaOH aqueous solution is the most dropwise added drop-wise to same volume 0.5mol/L
MgSO4Solution (v C3H8O3:v H2O=15:85), dropping process keeps being stirred vigorously, and drips complete follow-up continuous
Stirring 6 hours, then ageing 24 hours, centrifugation, wash three times with deionized water and dehydrated alcohol successively,
50 DEG C are dried, obtain micro-/receive compound flower-shaped self-supporting Mg (OH)2Microsphere；
Step 2, by 0.416g Mg (OH)2It is scattered in 75mL dehydrated alcohol (ultrasonic disperse 5min),
2.085g FeSO4·7H2O is dissolved in 75mL deionized water, and the two is moved into 500ml there-necked flask (concentration
(v dehydrated alcohol: v deionized water=1:1) FeSO for 0.05mol/L4Solution)；
Step 3, holding mechanical agitation 300r/min, be passed through N2Insulation blocking, then drips to there-necked flask
Add equal-volume (150mL) 0.25mol/L NaBH4Solution, drop rate 3mL/min, drip complete continuation and stir
Mixing 30min, reaction gained black solid is by centrifugation, and washing ethanol is washed three times successively, and 45 DEG C of vacuum are done
Dry 12h, obtains the Mg (OH) of theoretical negative carrying capacity 50%2The nano zero-valence iron composite material supported.
This example prepare micro-/receive compound flower-shaped self-supporting Mg (OH)2Microsphere surface morphology SEM characterizes such as
Shown in Fig. 1, the size of flower-like microsphere is at 10 microns, internal by the lamella intertexture of 10-20 nanometer thickness
Become.Mg(OH)2The surface topography SEM of the nano zero-valence iron composite material supported characterizes as in figure 2 it is shown, receive
Rice zero-valent iron particle uniform particle diameter, be uniformly dispersed, there is no agglomeration.
This case step one can be amplified easily, this laboratory realized feather weight synthesis, pattern, size with
Little trial product zero difference.Magnesium source, source of iron used by this example are all the elements that in the earth's crust, abundance is the highest, nature
A lot of natural minerals can raw material as an alternative, contribute to reducing further product cost.
Embodiment 2
Step one, same as in Example 1；
Step 2, by 0.832g Mg (OH)2It is scattered in 75mL dehydrated alcohol (ultrasonic disperse 5min),
2.085g FeSO4·7H2O is dissolved in 75mL deionized water, the two is moved into 500mL there-necked flask (dense
Degree is (v dehydrated alcohol: v deionized water=1:1) FeSO of 0.05mol/L4Solution)；
Step 3, holding mechanical agitation 300r/min, be passed through N2Insulation blocking, then drips to there-necked flask
Add equal-volume (150ml) 0.25mol/L NaBH4Solution, drop rate 3ml/min, drip complete continuation and stir
30min, reaction gained black solid is by centrifugation, and washing ethanol is washed three times successively, 45 DEG C of vacuum drying
12h, obtains the Mg (OH) of theoretical negative carrying capacity 33%2The nano zero-valence iron composite material supported.
Embodiment 3
Step one, same as in Example 1；
Step 2, by 0.208g Mg (OH)2It is scattered in 75mL dehydrated alcohol (ultrasonic disperse 5min),
2.085g FeSO4·7H2O is dissolved in 75ml deionized water, and the two is moved into 500ml there-necked flask (concentration
(v dehydrated alcohol: v deionized water=1:1) FeSO for 0.05mol/L4Solution)；
Step 3, holding mechanical agitation 300r/min, be passed through N2Insulation blocking, then drips to there-necked flask
Add equal-volume (150mL) 0.25mol/L NaBH4Solution, drop rate 3mL/min, drip complete continuation and stir
Mixing 30min, reaction gained black solid is by centrifugation, and washing ethanol is washed three times successively, and 45 DEG C of vacuum are done
Dry 12h, obtains the Mg (OH) of theoretical negative carrying capacity 67%2The nano zero-valence iron composite material supported.
Finally it is necessary described herein: above example is served only for making technical scheme into one
Step explains, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art according to
Some nonessential improvement and adjustment that the foregoing of the present invention is made belong to protection scope of the present invention.
Claims (7)
1. the preparation method of a loaded nano zero-valent iron composite material, it is characterised in that comprise the steps:
Prepare the most respectively micro-/receive compound flower-shaped self-supporting Mg (OH)2Microsphere, the water-ethanol mixed solution of ferrum/ferrous ion and sodium borohydride aqueous solution；
B. by described Mg (OH)2Microsphere joins in the water-ethanol mixed solution of described ferrum/ferrous ion, and ultrasonic making is uniformly dispersed, and obtains disperseing Mg (OH)2Ferrum/ferrous ions soln；
C. described sodium borohydride aqueous solution is added drop-wise to described dispersion Mg (OH) with the speed of 3mL/min2Ferrum/ferrous ions soln in, in-situ reducing ferrum/ferrous ion prepares Mg (OH)2The nano zero valence iron of load；
Wherein, described micro-/receive compound flower-shaped self-supporting Mg (OH)2The preparation method of microsphere is: be added drop-wise to by sodium hydrate aqueous solution in the water-propanol mixed solution of magnesium ion, dropping process keeps the stirring with 300r/min rotating speed, drip complete follow-up continuous stirring 6 hours, then ageing carried out centrifugation after 24 hours, taking precipitate carries out washing, is dried, obtain micro-/receive compound flower-shaped self-supporting Mg (OH)2Microsphere.
2. preparation method as claimed in claim 1, it is characterised in that described micro-/receive compound flower-shaped self-supporting Mg (OH)2In the preparation of microsphere, sodium hydroxide is 2:1 with the mol ratio of magnesium ion.
3. preparation method as claimed in claim 1, it is characterised in that in the water of described magnesium ion-propanol mixed solution, the volume ratio of water and propanol is 85:15.
4. preparation method as claimed in claim 1, it is characterised in that the concentration of described sodium borohydride aqueous solution is 0.25mol/L.
5. preparation method as claimed in claim 1, it is characterised in that the water-ethanol mixed solution of described ferrum/ferrous ion is by FeSO4·7H2O is dissolved in the mixed liquor of water and ethanol according to the concentration of ferrous ion 0.05mol/L and obtains.
6. preparation method as claimed in claim 1, it is characterised in that in described water-ethanol mixed solution, the volume ratio of water and dehydrated alcohol is 1:1.
7. preparation method as claimed in claim 1, it is characterised in that described Mg (OH)2Mass ratio 0.33～0.67 with Fe.
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| CN105289495B (en) * | 2015-11-19 | 2017-07-28 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Using adsorbing the method that the useless clay mineral reaction in-situ after dyestuff prepares multifunctional composite |
| CN105397106A (en) * | 2015-12-23 | 2016-03-16 | 上海大学 | Method of preparing nanoscale zero-valent iron particles through improved liquid phase reduction method |
| CN105562706A (en) * | 2015-12-23 | 2016-05-11 | 上海大学 | Method for preparing nanoscale zero-valent iron particles through polyvinylpyrrolidone (PVP) improved liquid phase reduction method |
| CN106166474B (en) * | 2016-08-17 | 2019-05-14 | 华南理工大学 | A kind of specific regulatory control nano zero valence iron corrosion product and the method for reinforcing nano zero valence iron adsorption of Low Concentration arsenic |
| CN107670646B (en) * | 2017-09-22 | 2020-03-10 | 中国科学院合肥物质科学研究院 | Beaded nano zero-valent iron/cellulose composite material and application thereof |
| CN110000371B (en) * | 2018-01-04 | 2022-12-30 | 清华大学 | Coated nano zero-valent iron and preparation method and application thereof |
| CN113649000B (en) * | 2021-06-29 | 2023-06-20 | 福建师范大学 | Honeycomb porous Fe/Mg (OH) 2 Catalytic material and preparation method thereof |
| CN114053881B (en) * | 2021-12-09 | 2024-04-05 | 上海源依青科技有限责任公司 | Preparation method of hydrogel filtering membrane for efficiently loading and catalyzing organic pollutants |
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