CN104759635A - Preparation method of load type nanometer zero-valent iron composite material - Google Patents
Preparation method of load type nanometer zero-valent iron composite material Download PDFInfo
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- CN104759635A CN104759635A CN201510107130.XA CN201510107130A CN104759635A CN 104759635 A CN104759635 A CN 104759635A CN 201510107130 A CN201510107130 A CN 201510107130A CN 104759635 A CN104759635 A CN 104759635A
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Abstract
The invention discloses a preparation method of a load type nanometer zero-valent iron composite material. The preparation method comprises the following steps: a) preparing a micro/nanometer grade composite flower-shaped self-supported Mg (OH) 2 microballoon' b) dispersing it to iron/ ferrous ion solution with certain concentration; c) dropwise adding sodium borohydride solution in the mixed solution, and restoring iron/ ferrous ion at original site to prepare Mg (OH) 2 loaded nanometer zero-valent iron. The preparation method has the following advantages: 1. the preparation method is soft in condition, simple in operation, green and environment-friendly and convenient to realize the quantitative production; 2, the raw material is wide in source and low in price, and good for reducing cost; 3, the load volume of the load type nanometer zero-valent iron is adjustable, the product shape is uniform and the dimension is controllable; 4, the nanometer zero-valent iron obtained by the invention has high-efficient removing ability for heavy metal ions, organic solution, dye and other environmental pollutants, and can be used as the water disposal agent in an environmental domain.
Description
Technical field
The present invention relates to a kind of preparation method of loaded nano zero-valent iron composite material, belong to field of inorganic nano material.
Background technology
Nano zero valence iron (nZVI), owing to having the advantages such as high-ratio surface, high activity, strong reducing property, is successfully applied to chloro organic cpd, nitroaromatic, dye well heavy metal contaminants in process underground water/waste water.Based on the underground water in-situ immobilization place of nZVI material in the whole world more than 20.But the activity that the reunion that the small particle diameter of nZVI and self magnetic cause causes, life-span and treatment effeciency sharply decline, and seriously hinder nZVI large-scale application.By nZVI load on other materials, can effectively solve the problem, the backing material reported comprises two classes: a class is natural minerals, as diatomite, bentonite, kaolinite, column clay etc.; Another kind of is synthetic material, as chelating resin, mesoporous carbon, silica, Graphene etc.Above-mentioned backing material can effectively disperse nZVI particle to a certain extent, but the preparation method had in them is complicated, and condition is harsh, expensive, cannot large-scale application; Natural minerals is drawn materials extensively, low price, but after load, pattern is uneven, can not play the maximal efficiency of nZVI.Conventional backing materials is the physics of Special attention will be given to material, chemical stability and mechanical strength often, generally only plays the effect of single carrier, for improving the dispersiveness of nano zero valence iron particle, reducing it and reuniting in the composite formed with nano zero valence iron.If backing material is while realizing its " carrier " function, itself there is the ability removing water pollutant, 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 of its application.
Nanometer Mg (OH)
2as a kind of low cost, eco-friendly water treatment agent, this shows good application prospect in aspects such as acid waste water process, heavy metal removing, decolorizing printing and dyeing waste waters, but it is confined to physical absorption and precipitation to the removal of pollutant, to obstinate organic matter and metal ion limited efficiency.The Mg (OH) of chemical precipitation method synthesis
2usually easily formed the flower-like structure of self-supporting by regulation and control, thus there is the potential good load capacity to nZVI of Large ratio surface sum.NZVI and Mg (OH)
2the combination of two kinds of environmental treatment materials 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 to the system of efficient removal ability.
Summary of the invention
A kind of liquid phase reduction is the object of the present invention is to provide to prepare the method for loaded nano Zero-valent Iron, the features such as the 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:
There is a preparation method for the loaded nano Zero-valent Iron compound of High-efficient Water handling property, comprise the steps:
A) micro-/flower-shaped self-supporting Mg of compound of receiving (OH) is prepared
2microballoon;
B) the water-ethanol mixed solution of iron/ferrous ion is prepared;
C) sodium borohydride solution is prepared;
D) by step a) the middle Mg (OH) prepared
2microballoon joins step b) in prepare in iron/ferrous ions soln, ultrasonic making is uniformly dispersed, obtain dispersion Mg (OH)
2iron/ferrous ions soln;
E) by step c) in the d that is added drop-wise to certain speed of the sodium borohydride solution that obtains) in the mixed solution prepared of step, in-situ reducing iron/ferrous ion prepares Mg (OH)
2the nano zero valence iron of load.
F) be separated by solid-liquid suspension e) obtained, the black solid of collection is product.
Preferably, described source of iron is FeSO
47H
2o, 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.
The invention has the advantages that:
1. utilize method disclosed by the invention to have mild condition, the feature that simple to operate, volume production is convenient in environmental protection to prepare loaded nano Zero-valent Iron;
2. the raw material sources that utilize of the present invention are extensive, cheap, are beneficial to and reduce costs;
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 dyestuff of obtaining of the present invention have efficient removal ability, can be used as water treatment agent for environmental area.
Accompanying drawing explanation
Fig. 1 embodiment of the present invention 1 obtain micro-/the flower-shaped self-supporting Mg of compound of receiving (OH)
2the electron scanning micrograph of microballoon;
Fig. 2 is the Mg (OH) of preparation in embodiment 1
2the nano zero-valence iron composite material photo supported.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.
Embodiment 1
Under step one, room temperature, the 1mol/L NaOH aqueous solution is slowly dropwise added drop-wise to same volume 0.5mol/LMgSO
4solution (v C
3h
8o
3: v H
2o=15:85), the process that drips keeps vigorous stirring, dropwises rear continuation stirring 6 hours, then ageing 24 hours, centrifugation, washes three times with deionized water and absolute ethyl alcohol successively, 50 DEG C of dryings, obtain micro-/receive the flower-shaped self-supporting Mg (OH) of compound
2microballoon;
Step 2, by 0.416g Mg (OH)
2be scattered in (ultrasonic disperse 5min) in 75ml absolute ethyl alcohol, 2.085g FeSO
47H
2o is dissolved in 75ml deionized water, and the two is moved into 500ml there-necked flask, and (concentration is (v absolute ethyl alcohol: v deionized water=1:1) FeSO of 0.05mol/L
4solution);
Step 3, maintenance mechanical agitation 300r/min, pass into N
2insulation blocking, then drips equal-volume (150ml) 0.25mol/L NaBH to there-necked flask
4solution, drop rate 3ml/min, dropwises and continues to stir 30min, and reaction gained black solid, by centrifugation, is washed ethanol successively and washed three times, 45 DEG C of vacuum drying 12h, obtain the Mg (OH) of theoretical negative carrying capacity 50%
2the nano zero-valence iron composite material supported.
This example prepare micro-/receive the flower-shaped self-supporting Mg (OH) of compound
2microsphere surface morphology SEM characterizes as shown in Figure 1, Mg (OH)
2the surface topography SEM of the nano zero-valence iron composite material supported characterizes as shown in Figure 2, and nano zero valence iron grain diameter is homogeneous, be uniformly dispersed, and does not have agglomeration.
This case step one can be amplified easily, and this laboratory has realized feather weight synthesis, pattern, size and little trial product indifference.This example magnesium used source, source of iron are all the elements that in the earth's crust, abundance is very high, and a lot of natural minerals of nature can be used as alternative materials, contribute to reducing product cost further.
Embodiment 2
Step one, identical with embodiment 1;
Step 2, by 0.832g Mg (OH)
2be scattered in (ultrasonic disperse 5min) in 75ml absolute ethyl alcohol, 2.085g FeSO
47H
2o is dissolved in 75ml deionized water, and the two is moved into 500ml there-necked flask, and (concentration is (v absolute ethyl alcohol: v deionized water=1:1) FeSO of 0.05mol/L
4solution);
Step 3, maintenance mechanical agitation 300r/min, pass into N
2insulation blocking, then drips equal-volume (150ml) 0.25mol/L NaBH to there-necked flask
4solution, drop rate 3ml/min, dropwises and continues to stir 30min, and reaction gained black solid, by centrifugation, is washed ethanol successively and washed three times, 45 DEG C of vacuum drying 12h, obtain the Mg (OH) of theoretical negative carrying capacity 33%
2the nano zero-valence iron composite material supported.
Embodiment 3
Step one, identical with embodiment 1;
Step 2, by 0.208g Mg (OH)
2be scattered in (ultrasonic disperse 5min) in 75ml absolute ethyl alcohol, 2.085gFeSO
47H
2o is dissolved in 75ml deionized water, and the two is moved into 500ml there-necked flask, and (concentration is (v absolute ethyl alcohol: v deionized water=1:1) FeSO of 0.05mol/L
4solution);
Step 3, maintenance mechanical agitation 300r/min, pass into N
2insulation blocking, then drips equal-volume (150ml) 0.25mol/L NaBH to there-necked flask
4solution, drop rate 3ml/min, dropwises and continues to stir 30min, and reaction gained black solid, by centrifugation, is washed ethanol successively and washed three times, 45 DEG C of vacuum drying 12h, obtain the Mg (OH) of theoretical negative carrying capacity 67%
2the nano zero-valence iron composite material supported.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (7)
1. a preparation method for loaded nano zero-valent iron composite material, is characterized in that, comprises the steps:
A. micro-/flower-shaped self-supporting Mg of compound of receiving (OH) is prepared respectively
2the water-ethanol mixed solution of microballoon, iron/ferrous ion and sodium borohydride aqueous solution;
B. by described Mg (OH)
2microballoon joins in the water-ethanol mixed solution of described iron/ferrous ion, and ultrasonic making is uniformly dispersed, and obtains dispersion Mg (OH)
2iron/ferrous ions soln;
C. described sodium borohydride solution is added drop-wise to described dispersion Mg (OH) with the speed of 3ml/min
2iron/ferrous ions soln in, in-situ reducing iron/ferrous ion prepares Mg (OH)
2the nano zero valence iron of load;
Wherein, described micro-/the flower-shaped self-supporting Mg of compound of receiving (OH)
2the preparation method of microballoon is: by sodium hydrate aqueous solution in the water-propyl alcohol mixed solution being added drop-wise to magnesium ion, dropping process keeps with the stirring of 300r/min rotating speed, dropwise rear continuation stirring 6 hours, then ageing carried out centrifugation after 24 hours, taking precipitate carries out washing, dry, obtain micro-/receive the flower-shaped self-supporting Mg (OH) of compound
2microballoon.
2. preparation method as claimed in claim 1, is characterized in that, described micro-/the flower-shaped self-supporting Mg of compound of receiving (OH)
2in the preparation of microballoon, the mol ratio of NaOH and magnesium ion is 2:1.
3. preparation method as claimed in claim 1, it is characterized in that, in the water-propyl alcohol mixed solution of described magnesium ion, the volume ratio of hydration propyl alcohol is 85:15.
4. preparation method as claimed in claim 1, it is characterized in that, the concentration of described sodium borohydride aqueous solution is 0.25mol/L.
5. preparation method as claimed in claim 1, it is characterized in that, the water-ethanol mixed solution of described iron/ferrous ion is by FeSO
47H
2o 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 characterized in that, in described water-ethanol mixed solution, the volume ratio of water and absolute ethyl alcohol is 1:1.
7. preparation method as claimed in claim 1, is characterized in that, described Mg (OH)
2with the mass ratio 0.33 ~ 0.67 of Fe.
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Cited By (8)
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| CN105289495A (en) * | 2015-11-19 | 2016-02-03 | 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 | Method for preparing multifunctional composite material by in situ reaction of waste clay mineral adsorbing dye |
| 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 |
| CN106166474A (en) * | 2016-08-17 | 2016-11-30 | 华南理工大学 | A kind of specific regulatory control nano zero valence iron corrosion product the method strengthening nano zero valence iron adsorption of Low Concentration arsenic |
| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
| CN110000371A (en) * | 2018-01-04 | 2019-07-12 | 清华大学 | A kind of nano zero valence iron of cladding and its preparation method and application |
| CN113649000A (en) * | 2021-06-29 | 2021-11-16 | 福建师范大学 | Honeycomb porous Fe/Mg (OH)2Catalytic material and preparation method thereof |
| CN114053881A (en) * | 2021-12-09 | 2022-02-18 | 天津工业大学 | Preparation method of hydrogel filtering membrane for efficiently loading catalytic organic pollutants |
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Cited By (14)
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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 |
| CN105289495A (en) * | 2015-11-19 | 2016-02-03 | 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 | Method for preparing multifunctional composite material by in situ reaction of waste clay mineral adsorbing dye |
| 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 |
| CN106166474A (en) * | 2016-08-17 | 2016-11-30 | 华南理工大学 | A kind of specific regulatory control nano zero valence iron corrosion product the method strengthening nano zero valence iron adsorption of Low Concentration arsenic |
| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
| 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 |
| CN110000371A (en) * | 2018-01-04 | 2019-07-12 | 清华大学 | A kind of nano zero valence iron of cladding and its preparation method and application |
| CN110000371B (en) * | 2018-01-04 | 2022-12-30 | 清华大学 | Coated nano zero-valent iron and preparation method and application thereof |
| CN113649000A (en) * | 2021-06-29 | 2021-11-16 | 福建师范大学 | Honeycomb porous Fe/Mg (OH)2Catalytic material and preparation method 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 |
| CN114053881A (en) * | 2021-12-09 | 2022-02-18 | 天津工业大学 | Preparation method of hydrogel filtering membrane for efficiently loading catalytic organic pollutants |
| 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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