CN103212370B - Zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material and preparation method thereof - Google Patents
Zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material and preparation method thereof Download PDFInfo
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Abstract
A kind of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material is provided in the present invention, provide the preparation method of this material simultaneously, this material is using the zeolite molecular sieve of natural or Prof. Du Yucang as base material, Nanoscale Iron Mn oxide is carried in the aperture of zeolite molecular sieve, and the quality of Nanoscale Iron Mn oxide accounts for 10% ~ 40 wt% in overall arsenic removal material, the specific area of this material is 280 ~ 342 m
2/ g; Described Nanoscale Iron Mn oxide is magnetic Nano iron and manganese oxides, therefore arsenic removal material provided by the present invention has by the characteristic of attraction, and in removal water, still keep magnetic before and after the pollutant such as arsenic, there is larger specific area and excellent arsenic removal performance.Meanwhile, the preparation method of this material is easy, and raw materials is cheap and easy to get, can remove the arsenic in water efficiently, realize good effect of separating solid from liquid, has important effect to the in-situ immobilization that the arsenic solved in water body pollutes.
Description
Technical field
The present invention relates to a kind of arsenic removal material be applied in underground water, particularly relate to a kind of by zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material, belong to water-treatment technology field.
Background technology
At present, the arsenic pollution problem in underground water is very general, and it has become international environmental problem, arsenic has cumulative bad and chronic toxicity, long term accumulation can directly be detrimental to health, and the sustainable development of impact society, arsenic removal technology is one of study hotspot of current environmental science.Drink Water jet cleaning sanitary standard (10 μ g/L) according to the up-to-date promulgation of China, the population that Drinking Water in China exceedes this standard is estimated to reach tens million of.
The most common with absorption method in dearsenicating method in water body, the method easily operates, with low cost.Arsenic removal material has active carbon, porous mineral materials, metal (hydrogen) oxide, industrial waste etc.Zeolite molecular sieve is a class nonmetallic mineral that is cheap, that have loose structure, take zeolite molecular sieve as carrier, loaded with nano iron and manganese oxides, and specific area improves greatly, and arsenic removal is rapid, and clearance is high, can reach drinking water standard limit value.And iron and manganese oxides, owing to having the function of oxidation and absorption, is suitable for being applied in the arsenic pollution amelioration of underground water.
Patent of invention " arsenic removal material of a kind of zeolite-loaded nanometer ferrimanganic binary oxide and preparation method thereof ", application number 201210038049 discloses a kind of arsenic removal material of zeolite-loaded nanometer ferrimanganic binary oxide, although this material has the effect of good place to go trivalent arsenic and pentavalent arsenic, but it has the following disadvantages: the iron in this material is+3 valencys, exist to be oxidized Iron activiation, not there is magnetic.After adsorbent arsenic removal, being still present in water body, to thoroughly remove the arsenic in solution, need to carry out follow-up Separation of Solid and Liquid, and the precipitation usually adopted, filter process being loaded down with trivial details.
Summary of the invention
The invention provides a kind of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material, provide the preparation method of this material simultaneously, arsenic removal material provided by the present invention has by the characteristic of attraction, and still keeps magnetic before and after the pollutant such as arsenic in removal water; It has larger specific area and excellent arsenic removal performance.Meanwhile, the preparation method of this material is easy, and raw materials is cheap and easy to get, can remove the arsenic in water efficiently, realize good effect of separating solid from liquid, has great importance to the in-situ immobilization that the arsenic solved in water body pollutes.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material, this material is using the zeolite molecular sieve of natural or Prof. Du Yucang as base material, Nanoscale Iron Mn oxide is carried in the aperture of zeolite molecular sieve, and the quality of Nanoscale Iron Mn oxide accounts for quality and accounts for 10% ~ 40 wt% in overall arsenic removal material, the specific area of this material is 280 ~ 342 m
2/ g; Described Nanoscale Iron Mn oxide is magnetic Nano iron and manganese oxides, and wherein in Nanoscale Iron Mn oxide, the mol ratio of ferro element and manganese element is 9:2.
Described zeolite molecular sieve is particle diameter >=100 object particle or powder.
Described Nanoscale Iron Mn oxide can trivalent arsenic in adsorbed water body and pentavalent arsenic trivalent arsenic is oxidized to pentavalent arsenic.
The preparation method of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material: comprise the following steps: (1), be fully dissolved in deionized water by polyvinylpyrrolidone, obtains solution A after heating water bath;
(2), in solution A add zeolite, fully after mixing, add ferrous salt solution, obtain solution B;
(3), by the pH value of solution B alkalescence is adjusted to, until produce green precipitate in solution B;
(4), use sprayer unit to be atomized permanganate solution, the permanganate solution after atomization is added in solution B, in the process added, solution B is slowly stirred, generate black precipitate, obtain solution C; In the permanganate solution added, in manganese element and solution B, the mol ratio of ferro element is 2:9;
(5), adjust the pH value of solution C between 9 ~ 12, make solution C keep stable colloidal state not precipitate;
(6), by aging for solution C water-bath 6-12 hour;
(7), deionized water and ethanol is adopted alternately fully to wash the solution C after aging and filter, by the sediment vacuum drying after filtering, namely obtained zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material.
In step (1), polyvinylpyrrolidone is fully dissolved into after in deionized water, leaves standstill 0.5-1 hour, then 90 DEG C of Water Under bath heating.
The sodium hydroxide solution of 2 ~ 4mol/L is adopted to regulate solution ph in step (2) and (5).
Described zeolite is zeolite after persalt washing also dry process.
Described permanganate solution sprays in solution B to spray into mode continuously in confined conditions.
In step (6), bath temperature is 70 ~ 90 DEG C.
In step (7), ethanol and deionized water replace washing times is 6-10 time; Vacuum drying temperature is 60 ~ 80 DEG C, and drying time is 18 ~ 24 hours.
In preparation method provided by the present invention, in preparation method provided by the present invention, by the fine dispersion agent effect of polyvinylpyrrolidone, make to cover ferrous ion in zeolite surface and hole, when permanganate pH be 9 ~ 12 and temperature 70 ~ 90 DEG C of water-baths under enter solution after, react with the ferrous ion of zeolite surface, generate the composite oxides of tri-iron tetroxide and manganese dioxide.Because tri-iron tetroxide has magnetic, the compound of it and manganese dioxide is carried on zeolite, makes the material prepared have magnetic.
The specific area of arsenic removal material provided by the invention is large, and arsenic removal speed is fast, and adsorption capacity is large.To the pollutant such as trivalent arsenic and pentavalent arsenic, there is excellent removal effect.And its preparation process is simple, with low cost, can be mass-produced.Meanwhile, arsenic removal material provided by the present invention has magnetic, and under the attraction of magnet, can move, before and after arsenic removal, the magnetic of material is constant, good effect of separating solid from liquid.
Accompanying drawing explanation
Fig. 1 is the solid-liquid separation effect figure of arsenic removal material prepared in the embodiment of the present invention 1;
Fig. 2 is magnetization curve (VSM) figure of the arsenic removal material that example 1,2,3 prepares;
Fig. 3 is ESEM-power spectrum (SEM-EDS) figure of the arsenic removal material that example 1 obtains;
Fig. 4 is that the obtained arsenic removal material of example 1 is to arsenious treatment effect figure;
Fig. 5 is that the obtained arsenic removal material of example 1 is to the treatment effect figure of pentavalent arsenic.
Detailed description of the invention
Below in conjunction with specific embodiment, detailed specific description is done to the present invention.
Embodiment 1
Choose particle diameter >=100 object zeolite hydrochloric acid to clean, for subsequent use after 105 DEG C of dryings.Take 10 grams of polyvinylpyrrolidones, be fully dissolved in 150mL deionized water, leave standstill after 45 minutes, then 70 DEG C of Water Under bath heating, obtain solution A.Take the dried zeolite of 0.25g, add in solution A, fully after mixing, add 4.97 grams of FeCl
24H
2o, obtains solution B; The pH value of the solution B sodium hydroxide solution of 2 mol/L is adjusted to alkalescence, until produce green precipitate in solution B.Then 0.8 g sodium permanganate is configured to the 100ml aqueous solution, sprayer unit is used to be atomized sodium permanganate solution, sodium permanganate solution after atomization is sprayed in solution B to spray into mode continuously in confined conditions, in the process added, solution B is slowly stirred, generate black precipitate, obtain solution C; The pH value of adjustment solution C is between 9 ~ 12, makes solution C keep stable colloidal state not precipitate.
By aging 8 hours of solution C water-bath at 70 DEG C, after removing supernatant, deionized water and ethanol is adopted alternately the solution C after aging fully to be washed to 10 times and filtered, by the sediment vacuum drying 24 hours under 60 DEG C of conditions after filtering, namely obtained zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material.
Arsenic removal material obtained in the present embodiment is tested through BET, can obtain: this zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material BET specific area is 342 m
2/ g.Carry out SEM-EDS test known: material particle size is nanoscale, and wherein the atomic ratio of iron and manganese is 9:2; By calculating of weighing to the zeolite before and after load, can obtain: the load capacity of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material is about 10 wt%.
Arsenic removal material obtained in the present embodiment is applied in removing arsenic in water, and concrete dearsenicating method is:
Be 2 mg/L in trivalent arsenic concentration, above-mentioned magnetic arsenic removal material is added with the use amount of 1g/L in the solution of pH 7.0, and in detection architecture arsenious concentration is over time, calculate trivalent arsenic clearance, the results are shown in Figure 4, as shown in Figure 4: in 1 hour, this magnetic arsenic removal material can reach 94% to clearance arsenious in water body, after 3 hours, all more than 99.6% is reached to arsenious clearance, during balance, trivalent arsenic concentration is lower than 10 μ g/L, because magnetic material is to arsenious oxidation, detect pentavalent arsenic in the solution, the pentavalent arsenic obtained because of oxidation in solution is finally removed, be add above-mentioned magnetic arsenic removal material with the use amount of 1g/L in the solution of 2 mg/L, pH 7.0 in pentavalent arsenic concentration, and in detection architecture the concentration of pentavalent arsenic is over time, calculate pentavalent arsenic clearance, the results are shown in Figure 5, from in Fig. 5: 1 hour, this magnetic arsenic removal material can reach 88.5% respectively to the clearance of pentavalent arsenic in water body, all reaches more than 99.2% after 3 hours to the clearance of pentavalent arsenic, and during balance, pentavalent arsenic concentration is lower than 10 μ g/L.
After arsenic removal material adsorption treatment, need the arsenic removal material in water body to isolate, to avoid polluting for 2 times.Because arsenic removal material obtained in the present embodiment is magnetic material, prove through test, under the effect of externally-applied magnetic field, namely realize adsorbent in 20 second time and be separated with water body, as shown in Figure 1.
Embodiment 2
Choose particle diameter >=100 object zeolite hydrochloric acid to clean, for subsequent use after 105 DEG C of dryings.Take 15 grams of polyvinylpyrrolidones, be fully dissolved in 225 mL deionized waters, leave standstill after 50 minutes, then 80 DEG C of Water Under bath heating, obtain solution A.Take the dried zeolite of 0.9g, add in solution A, fully after mixing, add 7.45 grams of FeCl
24H
2o, obtains solution B; The sodium hydroxide solution of the pH value 3mol/L of solution B is adjusted to alkalescence, until produce green precipitate in solution B.Then 1.32 g potassium permanganate are configured to the 150ml aqueous solution, sprayer unit is used to be atomized liquor potassic permanganate, liquor potassic permanganate after atomization is sprayed in solution B to spray into mode continuously in confined conditions, in the process added, solution B is slowly stirred, generate black precipitate, obtain solution C; The pH value of adjustment solution C is between 9 ~ 12, makes solution C keep stable colloidal state not precipitate.
By aging 12 hours of solution C water-bath at 80 DEG C, after removing supernatant, deionized water and ethanol is adopted alternately the solution C after aging fully to be washed to 10 times and filtered, by the sediment vacuum drying 18 hours under 80 DEG C of conditions after filtering, namely obtained zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material.
Arsenic removal material obtained in the present embodiment is tested through BET, can obtain: this zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material BET specific area is 311 m
2/ g.Carry out EDS test known: in material, the atomic ratio of iron and manganese is 9:2; By calculating of weighing to the zeolite before and after load, can obtain: the load capacity of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material is about 20wt%.
Embodiment 3
Zeolite hydrochloric acid is cleaned, for subsequent use after 105 DEG C of dryings.Take 20 grams of polyvinylpyrrolidones, be fully dissolved in 300mL deionized water, leave standstill after 60 minutes, then 90 DEG C of Water Under bath heating, obtain solution A.Take the dried zeolite of 2g, add in solution A, fully after mixing, add 13.9 grams of FeSO
47H
2o, obtains solution B; The sodium hydroxide solution of the pH value 4mol/L of solution B is adjusted to alkalescence, until produce green precipitate in solution B.Then 1.77 g potassium permanganate are configured to the 100ml aqueous solution, sprayer unit is used to be atomized liquor potassic permanganate, liquor potassic permanganate after atomization is sprayed in solution B to spray into mode continuously in confined conditions, in the process added, solution B is slowly stirred, generate black precipitate, obtain solution C; The pH value of adjustment solution C is between 9 ~ 12, makes solution C keep stable colloidal state not precipitate;
By aging 12 hours of solution C water-bath at 90 DEG C, after removing supernatant, deionized water and ethanol is adopted alternately the solution C after aging fully to be washed to 8 times and filtered, by the sediment vacuum drying 24 hours under 60 DEG C of conditions after filtering, namely obtained zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material.
Arsenic removal material obtained in the present embodiment is tested through BET, can obtain: this zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material BET specific area is 292 m
2/ g.Carry out EDS test known: in material, the atomic ratio of iron and manganese is 9:2; By calculating of weighing to the zeolite before and after load, can obtain: the load capacity of zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material is about 30wt%.
Claims (6)
1. a preparation method for zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material, this material is using the zeolite molecular sieve of natural or Prof. Du Yucang as base material, and described zeolite molecular sieve is particle diameter>=100 object powder; Nanoscale Iron Mn oxide is carried in the aperture of zeolite molecular sieve, and the quality of Nanoscale Iron Mn oxide accounts for 10 ~ 40 wt% in arsenic removal material, and the specific area of this material is 280 ~ 350 m
2/ g; Described Nanoscale Iron Mn oxide is magnetic Nano iron and manganese oxides, and wherein in Nanoscale Iron Mn oxide, the mol ratio of ferro element and manganese element is 9:2; Described Nanoscale Iron Mn oxide can trivalent arsenic in adsorbed water body and pentavalent arsenic trivalent arsenic is oxidized to pentavalent arsenic;
It is characterized in that described preparation method comprises the following steps: (1), be fully dissolved in deionized water by polyvinylpyrrolidone, after heating water bath, obtain solution A;
(2), in solution A add zeolite, fully after mixing, add ferrous salt solution, obtain solution B;
(3), by the pH value of solution B alkalescence is adjusted to, until produce green precipitate in solution B;
(4), use sprayer unit to be atomized permanganate solution, the permanganate solution after atomization is added in solution B, in the process added, solution B is slowly stirred, generate black precipitate, obtain solution C; In the permanganate solution added, in manganese element and solution B, the mol ratio of ferro element is 2:9;
(5), adjust the pH value of solution C between 9 ~ 12, make solution C keep stable colloidal state not precipitate;
(6), by aging for solution C water-bath 6-12 hour;
(7), deionized water and ethanol is adopted alternately fully to wash the solution C after aging and filter, by the sediment vacuum drying after filtering, namely obtained zeolite-loaded Nanoscale Iron Mn oxide magnetic arsenic removal material.
2. preparation method according to claim 1, is characterized in that: be fully dissolved into by polyvinylpyrrolidone in step (1) after in deionized water, leaves standstill 0.5-1 hour, then 70 ~ 90 DEG C of Water Under bath heating.
3. preparation method according to claim 1, is characterized in that: adopt the sodium hydroxide solution of 2 ~ 4mol/L to regulate solution ph in step (3) and (5).
4. preparation method according to claim 1, is characterized in that: described zeolite is zeolite after persalt washing also dry process.
5. preparation method according to claim 1, is characterized in that: in step (6), bath temperature is 70 ~ 90 DEG C.
6. preparation method according to claim 1, is characterized in that: in step (7), deionized water and ethanol replace washing times is 6-10 time; Vacuum drying temperature is 60 ~ 80 DEG C, and drying time is 18 ~ 24 hours.
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| CN103721671B (en) * | 2014-01-26 | 2016-01-27 | 中国地质大学（武汉） | A kind of nano magnetic iron oxide/kaolin particle and its production and use |
| CN104645932B (en) * | 2015-01-30 | 2016-09-14 | 暨南大学 | A kind of composite modified zeolite of iron and manganese oxides and preparation method and application |
| CN107537441A (en) * | 2017-09-23 | 2018-01-05 | 湖南大学 | A kind of nano-metal particle is modified the preparation and use of hydro-thermal Carbon Materials |
| CN107551998A (en) * | 2017-09-23 | 2018-01-09 | 湖南大学 | A kind of charcoal stabilizes the preparation method and application of iron and manganese oxides |
| CN110385141B (en) * | 2018-04-20 | 2021-05-04 | 武汉大学 | Composite catalyst for directly preparing aromatic hydrocarbon from synthesis gas and preparation method thereof |
| CN109879401A (en) * | 2019-03-09 | 2019-06-14 | 兰州交通大学 | A kind of folded plate artificial wetland system for strengthening nitrogen phosphorus ligands |
| CN110975794A (en) * | 2019-11-22 | 2020-04-10 | 昆明理工大学 | Iron-manganese composite oxide/Fe3O4Preparation method and application of core-shell material |
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