CN105148831A - Hangjin 2# soil loaded nano-zero valent iron adsorption material, preparation method and application - Google Patents
Hangjin 2# soil loaded nano-zero valent iron adsorption material, preparation method and application Download PDFInfo
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- CN105148831A CN105148831A CN201510381419.0A CN201510381419A CN105148831A CN 105148831 A CN105148831 A CN 105148831A CN 201510381419 A CN201510381419 A CN 201510381419A CN 105148831 A CN105148831 A CN 105148831A
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Abstract
The invention relates to a Hangjin 2# soil loaded nano-zero valent iron adsorption material, wherein the mass ratio of nano-zero valent iron to Hangjin 2# soil is 1:4-5. The preparation method employs Hangjin 2# soil as the carrier to load nano-zero valent iron, and the steps include: 1) dissolving an iron-containing oxide in an ethanol solution to obtain a mixed solution; 2) adding Hangjin 2# soil into the mixed solution of step 1, and controlling the mass ratio of nano-zero valent iron to Hangjin 2# soil at 1:4-5; 3) introducing nitrogen into the product of step 2, conducting stirring to remove oxygen; 4) adding a reducing agent into the product of step 3 to reduce the iron-containing oxide into nano-zero valent iron, and uniformly dispersing the nano-zero valent iron on the surface of the carrier material Hangjin 2# soil; and 5) subjecting the product obtained in step 4 to solid-liquid separation, and performing vacuum drying on the solid, thus obtaining the Hangjin 2# soil loaded nano-zero valent iron adsorption material. The adsorption material provided by the invention has higher reaction activity and reduction effectiveness, and has good application value in actual water pollution control and restoration projects.
Description
Technical field
The invention belongs to nano adsorption material field, relate to a kind of with the sorbing material of Hanggin 2# soil loaded with nano Zero-valent Iron particularly.
The invention still further relates to the preparation method of above-mentioned sorbing material.
The invention still further relates to the application of above-mentioned sorbing material.
Background technology
Because nano zero valence iron has, granularity is little, skin effect large, reactivity advantages of higher, it is a kind of excellent environment functional material, multiple pollutant matter in water body can be removed efficiently, as heavy metal ion, organic pollution etc., therefore using nano zero valence iron to remove water pollutant is a kind of new pollutant abatement technology grown up in recent years, be considered to the great innovation of water body, soil in-situ recovery technique, have larger application prospect.But nano zero valence iron also has following weak point in Synthesis and applications:
(1) specific area that nano zero valence iron is larger and stronger magnetic make it very easily reunite in preparations and applicatio process and form large particle, cause specific area to reduce, and active reduction, have impact on its using value to a great extent;
(2) agglomeration of nano zero valence iron particle also can reduce its mobile performance in water body, detergent is spread uneven, is difficult to contact completely with pollutant, reduces the possibility of its practical engineering application;
(3) high activity of nano zero valence iron also makes it be easy to be oxidized by non-targeted pollutant in environment (as water and oxygen), " spontaneous combustion " of i.e. nano zero valence iron, this phenomenon causes Zero-valent Iron reactivity and validity reduces, polluter in environment of can not degrading enduringly.
Therefore, for avoiding a large amount of reunions of nano zero valence iron, improve the reactivity of nano zero valence iron, strengthen its stability, prevent particle agglomeration, domestic and international scientific research personnel often selects some loads as dispersant in its preparations and applicatio process, and inorganic mineral becomes the preferred material of nano zero valence iron load carriers.This type of support materials mainly comprises: silica, aluminium oxide, zeolite, shitosan, kaolin, montmorillonite etc.These loads can alleviate the reunion of Nanoscale Iron to a certain extent, achieve good effect in pollutant removal.But, also there is following problem:
(1) reactivity and the reduction validity of the load Zero-valent Iron of synthesizing also need further raising.
(2) fractional load raw material sources are limited, and cost of material is high;
(3) load raw material particle size is large, and in order to improve reactivity, use more small particle diameter clay, need grind it and screen, pre-processing requirements is high;
(4) support materials absorption/flocculating property itself is limited, most without catalytic performance, how better to play the reduction/absorption/catalyzing cooperation effect of material, improves its clearance to pollutant, need to further investigate exploitation further.
Hanggin 2# soil is the end of the nineties in last century, is found in Ordos City, Inner Mongolia Autonomous Region Hangjin Banner, a kind of that combine for essential mineral with attapulgite, illite, chlorite, feldspar, calcite stone, containing the NEW TYPE OF COMPOSITE clay of rare earth element.Tentatively detecting reserves is 8,250,000 tons.GeneraI investigation reserves 3.4 hundred million tons; Integrated distribution is in 20 to 30 square kilometres, and prospective reserves is 1,000,000,000 tons.Hanggin 2# soil is in brownish red, and immersion mud is in " jelly sample ", and be difficult to dehydration, natural particle size less (average grain diameter of most sample is between 2.381 ~ 6.366 microns), specific area is large.Because negative electrical charge effective in Hanggin 2# soil adsorbs a certain amount of metal cation, make Hanggin 2# soil have certain cation exchange capacity, coloured organic macromolecule can be adsorbed simultaneously, there is good decoloring ability.It has good adsorptivity, ion interchangeability and dewatering, in sorbent material exploitation, have good DEVELOPMENT PROSPECT, applies very extensive.
Summary of the invention
The object of this invention is to provide a kind of with the sorbing material of Hanggin 2# soil loaded with nano Zero-valent Iron.
Another object of the present invention is to provide a kind of method preparing above-mentioned sorbing material.
For achieving the above object, the sorbing material of Hanggin soil 2# soil loaded with nano Zero-valent Iron provided by the invention, wherein, the mass ratio of nano zero valence iron and Hanggin 2# soil is 1:4-5.
The method of the above-mentioned sorbing material of preparation provided by the invention, be native for carrier loaded nano zero valence iron with Hanggin 2#, step is:
1) oxides-containing iron is dissolved in ethanolic solution, obtains mixed liquor;
2) in the mixed liquor of step 1, add Hanggin 2# soil, nano zero valence iron and Hanggin 2# soil mass ratio are 1:4-5;
3) in the product of step 2, pass into nitrogen, stir and remove oxygen;
4) product to step 3 adds reducing agent, and oxides-containing iron is reduced into nano zero valence iron, and is dispersed in carrier material Hanggin 2# soil surface;
5) product step 4 obtained carries out Separation of Solid and Liquid, solid vacuum drying, obtains the sorbing material of Hanggin soil 2# soil loaded with nano Zero-valent Iron.
Described method, wherein, Hanggin 2# soil grinds to form 200 mesh sieves in advance.
Described method, wherein, oxides-containing iron is FeCl
36H
2o.
Described method, wherein, reducing agent is sodium borohydride.
Described method, wherein, after step 5 is separated the solid absolute ethanol washing obtained, in 75 DEG C of vacuum drying.
Described method, wherein, the sorbing material of the Hanggin soil 2# soil loaded with nano Zero-valent Iron that step 5 obtains is kept in nitrogen atmosphere and prevents it by oxygen.
Sorbing material of the present invention can be applied in water pollution control recovery project.
Beneficial effect of the present invention is:
1) support materials Hanggin 2# soil reserves are large, distant view oil in place is 1,000,000,000 tons, exploitation easily, composite preparation can be directly applied to after coarse crushing, considerably reduce cost of material, and Hanggin 2# soil resource utilization rate can be significantly improved, improve the self-value of Hanggin 2# soil, significant economic worth will be produced.
2) Hanggin 2# soil loaded with nano Zero-valent Iron advanced composite material (ACM) provided by the invention, effectively can overcome the shortcomings such as nano zero valence iron is easily reunited, oxidizable, easy precipitation, manufacture process is pollution-free, environmental protection, there is well dispersed and stability, distribution of particles is more even, not easily forms particle agglomeration and autoxidation; There are better suspension and stability in aqueous; There is stronger oxidative degradation ability to environmental pollutants, longer effective reaction time, higher adsorption capacity.This material effectively can reduce nano zero valence iron (NZVI) dosage simultaneously, thus reduces reaction cost.
3) Hanggin soil is stronger with the collaborative coupling of Zero-valent Iron.Hanggin 2# clay mineral immersion mud is in " jelly sample ", and be difficult to dehydration, granularity is little, and surface area is large, has good ion-exchange capacity and adsorption capacity.Be rich in Fe simultaneously
2o
3, FeO, MgO, CaO, Al
2o
3, MnO, the Multimetal oxide such as rare earth element, the rare earth wherein contained comprises: La
2o
3,ce
2o
3,pr
2o
3,nd
2o
3,sm
2o
3deng, the total amount of rare earth oxide changes between 158.96 ~ 224.14 μ g/g, average out to 189.91 μ g/g.The special composition of Hanggin soil ensure that Hanggin 2# soil load Zero-valent Iron is while possessing reducing power, also there is excellent physical absorption performance and chemical flocculation effect and certain catalytic performance, therefore the material synthesized has reduction/absorption simultaneously, flocculation and catalytic action.
4) other clay loaded with nano Zero-valent Iron is compared, Hanggin 2# soil loaded with nano Zero-valent Iron advanced composite material (ACM) provided by the invention has higher reactivity and reduction validity. Hanggin 2# soil loaded with nano Zero-valent Iron advanced composite material (ACM) provided by the invention, not only there is the absorption property that Hanggin 2# soil is excellent simultaneously, the commutative performance of ion and decoloration performance, and the strong reducing action of nano zero valence iron can be given full play to and react the strong oxidation of the hydroxyl radical free radical (OH) produced with water, thus play absorption, oxidation, the pollutant removal synergy of reduction, to contaminant degradation, there is great catalysed promoted effect, pollutant effect is removed in the simple and mechanical mixing that contaminant removal efficiency is significantly higher than nano zero valence iron and Hanggin soil, also be significantly higher than to add separately nano zero valence iron and add separately Hanggin 2# soil and remove pollutant effect, various wastewater treatment can be widely used in, comprise and be applied to process containing heavy metal, dyeing waste water, in organic wastewater. for environmental contaminants are (as heavy metal, large molecular dye and halo organic pollution etc.) deep purifying and security control good technical support is provided.This material is expected to be used widely in actual environment pollution control and repair process.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of Hanggin soil 2# loaded with nano Zero-valent Iron (NZVI).
Detailed description of the invention
The present invention uses Hanggin clay mineral for template (carrier), and under normal temperature liquid phase environment, Hanggin 2# soil loaded nano Zero-valent Iron composite magnetic is prepared in reduction.The cation exchange capacity (CEC) that Hanggin 2# is larger can by Fe
3+adsorb and be scattered in bear electricity place, clay pit nitride layer surface, in reduction process, clay layer surface electrostatic power can limit contact between iron atom and a large amount of reunions, Zero-valent Iron is existed, the reactor synthesized as (Asia) nanoscale zero-valent iron atom cluster (particle) by Hanggin soil or carrier with amorphous polyatom bunch form.The generation that this preparation method not only can avoid Zero-valent Iron to reunite in building-up process, and the Zero-valent Iron of synthesis is more non-loaded or other Supported Nano Zero-valent Irons have less particle diameter, larger specific area, estimates to have higher reactivity.And, have and have stronger absorption property compared with the Hanggin 2# soil stone of bigger serface to organic in water body and inorganic pollution material.Utilize organic and inorganic pollutant in Hanggin 2# soil clay load-type zero-valent iron material height reducing activity, high adsorption removal reproducibility water body simultaneously.
In order to overcome above-mentioned nano zero valence iron in actual use easily reunite, oxidizable, easily precipitate, reactivity is low with reduction validity, the cost of material of load is high, pollutants removal rate is needed to the problems such as further raising, the invention provides one and can make full use of novel clay soil Hanggin 2# soil space surface, with Hanggin 2# soil for carrier material, liquid phase reduction original position is adopted to prepare high reaction activity, the method for high reduction validity Hanggin 2# soil loaded with nano Zero-valent Iron advanced composite material (ACM) and application.
The preparation method of Hanggin 2# soil loaded nano Zero-valent Iron is: under nitrogen atmosphere condition, by additional reducing agent sodium borohydride (NaBH
4) reduction, make oxides-containing iron (FeCl
36H
2o) be reduced into nano zero valence iron, and be dispersed in carrier material Hanggin 2# soil surface.Comprise the steps:
1) by the FeCl of 1.932g
36H
2o is dissolved in 50ml ethanolic solution (40ml ethanol, 10ml water), obtains mixed liquor.
2) by the mixed liquor of step 1 in there-necked flask, and add through simply ground 200 mesh sieves 2.00g Hanggin soil.Nano zero valence iron (NZVI) is made to be 1:4-5 with Hanggin 2# soil mass ratio.
3) in the product of step 2, pass into nitrogen magnetic agitation 30 minutes, remove the oxygen in mixed liquor.
4) 0.708g reducing agent (as sodium borohydride) is dissolved in solution 100ml water, sodium borohydride solution is transferred in 250ml pear-shaped flask.
5) Keep agitation and pass into nitrogen condition under, the sodium borohydride solution of step 4 is added in the product of step 3 with the rate of addition of 2-3 drop/sec, reaction terminate rear continuation stirring 20 minutes, mixing speed is 250 revs/min.
6) product obtained in step 5 is carried out Separation of Solid and Liquid, the solid obtained uses absolute ethanol washing 3 times, by solid 75 DEG C of dried in vacuo overnight, obtaining black solid is with Hanggin 2# soil for the nano zero-valence iron composite material of carrier, and sample is kept in nitrogen atmosphere before using and prevents it by oxygen.
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here does not limit the present invention, one of skill in the art can make improvements according to spirit of the present invention and change, these described improvement and change all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.
Embodiment 1: the preparation of Hanggin soil 2# loaded with nano Zero-valent Iron
The Hanggin 2# soil main chemical compositions content that the present embodiment adopts is as table 1.
1) by the FeCl of 1.932g
36H
2o is dissolved in 50ml ethanolic solution (40ml ethanol, 10ml water), obtains mixed liquor.
2) by the mixed liquor in step 1 in there-necked flask, and add through simply ground 200 mesh sieves 2.00g Hanggin soil.Nano zero valence iron (NZVI) is made to be 1:5 with Hanggin 2# soil mass ratio.
3) pass into nitrogen magnetic agitation 30 minutes in the product of step 2, remove the oxygen in mixed liquor.
4) 0.708g sodium borohydride is dissolved in solution 100ml water, sodium borohydride solution is transferred in 250ml pear-shaped flask.
5) Keep agitation and pass into nitrogen condition under, the sodium borohydride solution of step 4 is added in the product of step 3 with the rate of addition of 2-3 drop/sec, reaction terminate rear continuation stirring 20 minutes, mixing speed is 250 revs/min.
6) product step 5 obtained carries out Separation of Solid and Liquid, the solid obtained uses absolute ethanol washing 3 times, by solid 75 DEG C of dried in vacuo overnight, obtaining black solid is with Hanggin 2# soil for the nano zero-valence iron composite material of carrier, and sample is kept in nitrogen atmosphere before using and prevents it by oxygen.
As shown in Figure 1, its reactivity and reduction validity reach 93% to the scanning electron microscope (SEM) photograph of Hanggin soil 2# loaded with nano Zero-valent Iron (NZVI) prepared by the present embodiment after measured.
Embodiment 2: Hanggin soil loaded with nano Zero-valent Iron materials application is in methyl orange
Get 100ml and newly configure the methyl orange standard solution of 50mg/L in 250ml beaker, add in methyl orange solution by the composite NZVIHJ of synthesis, methyl orange initial concentration is 50mg/L, and composite dosage is 5g/L, NZVI Hanggin 2# soil duty factor is 1:5.Continuous stirring, rotating speed is 250 revs/min, sampling 1ml respectively at 30s, 1min, 2min, 3min, 4min, 5min, 6min, 9min, 12min, 15min, 20min, 25min, 30min, 40min adds in 25ml colorimetric cylinder, constant volume, ultraviolet specrophotometer is used to measure its absorbance, compared with stoste absorbance, the Hanggin soil loaded with nano Zero-valent Iron of research synthesis is to the effect removing methyl orange.Experimental result showed: the Hanggin soil loaded with nano Zero-valent Iron of synthesis just can reach the clearance of more than 95% to methyl orange at 10 minutes, be significantly higher than Hanggin soil and nano zero valence iron mechanical mixture under the same terms and remove the effect (58%) of methyl orange, also Hanggin soil (43%) independent under being significantly higher than the same terms, independent nano zero valence iron removes methyl orange effect (38%).
Table 1
| Constituent | SiO 2 | Al 2O 3 | GaO | Fe 2O 3 | MgO | Na 2O | K 2O | SO 3 |
| Mass fraction (%) | 52.51 | 18.42 | 9.04 | 7.82 | 3.83 | 0.54 | 4.43 | 0.56 |
Claims (8)
1. a sorbing material for Hanggin 2# soil loaded with nano Zero-valent Iron, wherein, the mass ratio of nano zero valence iron and Hanggin 2# soil is 1:4-5.
2. prepare the method for sorbing material described in claim 1, be native for carrier loaded nano zero valence iron with Hanggin 2#, step is:
1) oxides-containing iron is dissolved in ethanolic solution, obtains mixed liquor;
2) in the mixed liquor of step 1, add Hanggin 2# soil, nano zero valence iron and Hanggin 2# soil mass ratio are 1:4-5;
3) in the product of step 2, pass into nitrogen, stir and remove oxygen;
4) product to step 3 adds reducing agent, and oxides-containing iron is reduced into nano zero valence iron, and is dispersed in carrier material Hanggin 2# soil surface;
5) product step 4 obtained carries out Separation of Solid and Liquid, solid vacuum drying, obtains the sorbing material of Hanggin soil 2# soil loaded with nano Zero-valent Iron.
3. method according to claim 2, wherein, Hanggin 2# soil grinds to form 200 mesh sieves in advance.
4. method according to claim 2, wherein, oxides-containing iron is FeCl
36H
2o.
5. method according to claim 2, wherein, reducing agent is sodium borohydride.
6. method according to claim 2, wherein, after step 5 is separated the solid absolute ethanol washing obtained, in 75 DEG C of vacuum drying.
7. method according to claim 2, wherein, the sorbing material of the Hanggin soil 2# soil loaded with nano Zero-valent Iron that step 5 obtains is kept in nitrogen atmosphere and prevents it by oxygen.
8. the application of sorbing material according to claim 1 in water pollution control recovery project.
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Cited By (6)
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| CN106976942A (en) * | 2017-04-18 | 2017-07-25 | 河海大学 | A kind of organic polymer coargulator modified Nano Zero-valent Iron and its preparation method and application |
| CN110369483A (en) * | 2019-07-03 | 2019-10-25 | 湖南工业大学 | A kind of method of in-situ immobilization Heavy-Metal-Contaminated Environments soil |
| CN110369482A (en) * | 2019-07-03 | 2019-10-25 | 湖南工业大学 | A kind of method of repairing environment hormone contaminated soil |
| CN111019663A (en) * | 2019-12-24 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Heavy metal passivation material of nano zero-valent iron composite attapulgite, preparation method and application thereof |
| CN111019664A (en) * | 2019-12-26 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Method for preparing soil heavy metal passivation material by using palygorskite loaded with nano zero-valent iron |
| CN111252845A (en) * | 2020-02-24 | 2020-06-09 | 广东工业大学 | Novel catalysis-adsorption material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106976942A (en) * | 2017-04-18 | 2017-07-25 | 河海大学 | A kind of organic polymer coargulator modified Nano Zero-valent Iron and its preparation method and application |
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| CN111019664A (en) * | 2019-12-26 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Method for preparing soil heavy metal passivation material by using palygorskite loaded with nano zero-valent iron |
| CN111252845A (en) * | 2020-02-24 | 2020-06-09 | 广东工业大学 | Novel catalysis-adsorption material and preparation method and application thereof |
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