CN103464113A - Composite modified bentonite, as well as preparation method and application thereof - Google Patents
Composite modified bentonite, as well as preparation method and application thereof Download PDFInfo
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- CN103464113A CN103464113A CN2013104317035A CN201310431703A CN103464113A CN 103464113 A CN103464113 A CN 103464113A CN 2013104317035 A CN2013104317035 A CN 2013104317035A CN 201310431703 A CN201310431703 A CN 201310431703A CN 103464113 A CN103464113 A CN 103464113A
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Abstract
The invention discloses a composite modified bentonite. The composite modified bentonite is prepared by adopting chitosan to carry out loading on the modified bentonite chelated by ethanediamine. The composite modified bentonite can be used as a heavy-metal composite fixing agent, is applied in treating pollution caused by leaching of heavy metals in tailings and is large in fixing capacity of the heavy metals and strong in fixing capability of the heavy metals. Proved by experiment, if the composite modified bentonite is used for treating the tailings, not only the leaching amount of zinc in the tailings can be reduced by 57%-83%, but also the zinc in the leaching liquid of the tailings has good absorbing action (62-97%); simultaneously, the composite modified bentonite is simple in preparation process, low in cost and moderate in condition and is suitable for treating the pollution caused by the tailings at a mine area.
Description
Technical field
The invention belongs to the modified alta-mud technical field, relate in particular to a kind of composite modified bentonite and its preparation method and application.
Background technology
China is having the mineral resources than horn of plenty, and annual mining all is accompanied by a large amount of mine tailings and produces.Under the acid precipitation condition, heavy metal (as zinc, manganese etc.) more easily leaches from mine tailing.The heavy metal of these releases can enter in water body or soil along with environmental change, and the Eco-Environment System around mine is caused and has a strong impact on, and harm humans is healthy.Therefore, finding effective ways reply mining area mine tailing heavy metal pollution has great significance.
The method of controlling at present mine tailing heavy metal pollution mainly contains: bactericide method, neutralisation, covering isolation method and passivation coating method.In the control procedure of heavy metal pollution of mine, using the heavy metal fixative is one of important control method.This method can suppress Leaching of Heavy Metals from source, and cost is lower, convenient and easy, and the requirement that the fine satisfied improvement heavy metals mining area of energy pollutes, guarantee that its surrounding enviroment ecosystem is not contaminated.
Bentonite is a kind of clay mineral that montmorillonite is main component of take, abundant at China's reserves, cheap.Modified alta-mud is reaching containing report in the waste water treating agent of heavy metal more as the Adsorption of Organic agent.But most of modifier prices are higher, and treatment effect is little than the original soil raising, so find convenient, efficient, economic novel heavy metal fixative, seems particularly important.
Summary of the invention
The technical problem to be solved in the present invention is to provide composite modified bentonite of a kind of with low cost, economical and efficient and its preparation method and application, this composite modified bentonite can be used as the compound fixative of heavy metal, be applied to the pollution control of mine tailing Leaching of Heavy Metals, large to the fixed capacity of heavy metal, crystallized ability is strong.
For solving the problems of the technologies described above, the present invention by the following technical solutions: composite modified bentonite adopts shitosan carry out load and make the modified alta-mud through the ethylenediamine chelating.
Shitosan, ethylenediamine, bentonitic mass/volume/mass ratio are 1～2g:1～4mL:5～15g.
The preparation method of above-mentioned composite modified bentonite comprises the following steps:
<1 > get sodium bentonite and add the water stirring, be made into 10% suspension;
<2 > in 60～80 ℃ of water-baths, to step<1 > suspension in slowly add the pure ethylenediamine of analysis of 1～4mL, the limit edged stirs;
<3 > take in the acetum that 1～2g shitosan is dissolved in mass concentration 2%, be made into the chitosan solution of mass concentration 1～2%, stirring is dissolved fully to transparent clarification shitosan, then lentamente chitosan solution is added drop-wise to step<2 > mixed solution in, the loading process of shitosan carries out 2h in 80 ℃ of water-baths; Be cooled to again room temperature, wash 5 times after suction filtration, by gained filter cake heat drying in 60 ℃ of baking ovens, grind, cross 200 mesh sieves, obtain composite modified bentonite.
Above-mentioned composite modified bentonite is the application aspect heavy metal in fixing mine tailing.
Heavy metal is zinc.
Above-mentioned application, by following operating procedure, use:
<1 > immobilization of mine tailing is processed
Composite modified bentonite is added in the 5mL deionized water, be made into the suspension of mass concentration 2～50%, evenly be added drop-wise to 50g mine tailing surface, place ventilation 48h, until suspension volatilizes;
<2 > reaction
Add deionized water by mass volume ratio 1:10 in the mine tailing after immobilization, regulate pH to 4, gained mineral water mixture is put to 200rpm/min concussion 12h on the isothermal vibration device.
According to claim 6 application, also comprise following operating procedure:
<3 > measurement of heavy metal zinc in mine tailing
From step<2 > the mineral water mixture sample, centrifugal mistake 0.45 μ m filter membrane, utilize inductive coupling plasma emission spectrograph to measure the content of zinc in deionized water.The leaching amount of zinc reduces percentage and calculates as follows:
Wherein, the reduction degree of L-zinc leaching amount, X
before fixing-zinc leaching amount in mine tailing while not adding fixative, X
after fixingzinc leaching amount in mine tailing after-interpolation fixative.
The problem that lacks good heavy metal fixative for current mine tailing Heavy Metal Pollution Control, it is raw material that the inventor be take bentonite cheap and that reserves are abundant, take heavy metal chelant ethylenediamine and environmentally friendly natural polysaccharide shitosan is modifier, has made a heavy metal species composite solid and has determined agent---composite modified bentonite.Because ethylenediamine enters between bentonite bed, increased the original soil interlamellar spacing, and utilize shitosan and bentonitic characterization of adsorption, by chitosan loaded on the bentonite surface, both overcome the secondary environmental pollution that a large amount of ethylenediamine modification of independent use may cause, can overcome again the problem that cost that independent use shitosan brings increases, both are common uses the effect of fixing heavy metal more excellent.Experiment showed, and use composite modified bentonite of the present invention to process mine tailing, can make the leaching amount decrease (57～83%) of zinc in mine tailing.Simultaneously, preparation technology of the present invention is simple, with low cost, mild condition, is suitable for the mining area tailings pollution and administers.
The specific embodiment
Embodiment 1
<1 > get the 5g sodium bentonite and add the water stirring, be made into 10% suspension;
<2 > in 80 ℃ of water-baths, to step<1 > suspension in slowly add the pure ethylenediamine of analysis of 4mL, the limit edged stirs;
<3 > take in the acetum that the 2g shitosan is dissolved in mass concentration 2%, be made into the chitosan solution of mass concentration 2%, stirring is dissolved fully to transparent clarification shitosan, then lentamente chitosan solution is added drop-wise to step<2 > mixed solution in, drip off half an hour, and the loading process of shitosan carries out 2h in 80 ℃ of water-baths; Be cooled to again room temperature, wash 5 times after suction filtration, by gained filter cake heat drying in 60 ℃ of baking ovens, grind, cross 200 mesh sieves, obtain composite modified bentonite.
Embodiment 2
<1 > get the 15g sodium bentonite and add the water stirring, be made into 10% suspension;
<2 > in 60 ℃ of water-baths, to step<1 > suspension in slowly add the pure ethylenediamine of analysis of 1mL, the limit edged stirs;
<3 > take in the acetum that the 1g shitosan is dissolved in mass concentration 2%, be made into the chitosan solution of mass concentration 1%, stirring is dissolved fully to transparent clarification shitosan, then lentamente chitosan solution is added drop-wise to step<2 > mixed solution in, drip off half an hour, and the loading process of shitosan carries out 2h in 80 ℃ of water-baths; Be cooled to again room temperature, wash 5 times after suction filtration, by gained filter cake heat drying in 60 ℃ of baking ovens, grind, cross 200 mesh sieves, obtain composite modified bentonite.
Embodiment 3
<1 > get the 10g sodium bentonite and add the water stirring, be made into 10% suspension;
<2 > in 60 ℃ of water-baths, to step<1 > suspension in slowly add the pure ethylenediamine of analysis of 4mL, the limit edged stirs;
<3 > take in the acetum that the 2g shitosan is dissolved in mass concentration 2%, be made into the chitosan solution of mass concentration 2%, stirring is dissolved fully to transparent clarification shitosan, then lentamente chitosan solution is added drop-wise to step<2 > mixed solution in, drip off half an hour, and the loading process of shitosan carries out 2h in 80 ℃ of water-baths; Be cooled to again room temperature, wash 5 times after suction filtration, by gained filter cake heat drying in 60 ℃ of baking ovens, grind, cross 200 mesh sieves, obtain composite modified bentonite.
Embodiment 4
<1 > get the 10g sodium bentonite and add the water stirring, be made into 10% suspension;
<2 > in 70 ℃ of water-baths, to step<1 > suspension in slowly add the pure ethylenediamine of analysis of 3mL, the limit edged stirs;
<3 > take in the acetum that the 1.5g shitosan is dissolved in mass concentration 2%, be made into the chitosan solution of mass concentration 1.5%, stirring is dissolved fully to transparent clarification shitosan, then lentamente chitosan solution is added drop-wise to step<2 > mixed solution in, drip off half an hour, and the loading process of shitosan carries out 2h in 80 ℃ of water-baths; Be cooled to again room temperature, wash 5 times after suction filtration, by gained filter cake heat drying in 60 ℃ of baking ovens, grind, cross 200 mesh sieves, obtain composite modified bentonite.
The adsorption applications of zinc in 1 pair of tailing leaching liquid of application examples
The tailing leaching liquid soaked 30 days by deionized water of take is working solution, measure the 50mL working solution in the 100mL conical flask with the 50mL graduated cylinder, take 0.05,0.1,0.2, composite modified bentonite and the unmodified bentonite of 0.3g embodiment 2 add in above-mentioned working solution, regulating pH is 5.6,200r/min absorption 150min.Centrifugal rear mistake 0.45 μ m filter membrane, measure zinc concentration.
The results are shown in Table 1.
The absorption result of zinc in table 1 tailing leaching liquid
As can be seen from Table 1, at the bentonite dosage, during in low concentration, the effect of composite modified bentonite will obviously be better than unmodified bentonite.
Application examples 2
The somewhere mill tailings, after testing, wherein the content of heavy metal element zinc is the highest, and content is 3555m
g/ k
g.By following operating procedure, use the composite modified bentonite of embodiment 3 to be processed:
<1 > immobilization of mine tailing is processed
Unmodified bentonite and composite modified bentonite are added in the 5mL deionized water, be made into the suspension of mass concentration 2～50%, evenly be added drop-wise to 50g mine tailing surface, place ventilation 48h, until suspension volatilizes;
<2 > reaction
Add deionized water by mass volume ratio 1:10 in the mine tailing after immobilization, regulate pH to 4, gained mineral water mixture is put to 200rpm/min concussion 12h on the isothermal vibration device.
<3 > measurement of heavy metal zinc in mine tailing
From step<2 > the mineral water mixture sample, centrifugal mistake 0.45 μ m filter membrane, utilize inductive coupling plasma emission spectrograph to measure the content of zinc in deionized water.
The results are shown in Table 2.
Table 2 is the result of heavy metal zinc in mine tailing fixedly
Unmodified bentonite and composite modified bentonite have certain effect to the leaching of zinc in mine tailing as shown in Table 2, but, under the effect of different quality concentration suspension, composite modified bentonite all is better than unmodified bentonite.
The fixing application of zinc in 3 pairs of mine tailings of application examples
The composite modified bentonite of embodiment 4 and unmodified bentonite 0.1g, 0.5g, 1.5g, 2g, 2.5g are added in the 5mL deionized water, be made into successively 2%, 10%, 30%, 40%, 50% suspension, evenly be added drop-wise to respectively 50g mine tailing surface, place 48h at the shady and cool ventilation place, by regulating the deionized water that pH is 4 (simulation acidity larger acid rain) 500mL, join in immobilized mine tailing, put into the speed concussion 12h of oscillator with 200r/min, and maintenance moisture, regulate pH every one hour and make pH remain unchanged.After 12h, 0.45 μ m filter membrane is crossed in centrifugation, measures zinc concentration in leachate.
The results are shown in Table 3.
Table 3 is the result of heavy metal zinc in mine tailing fixedly
Unmodified bentonite and composite modified bentonite have certain effect to the leaching of zinc in mine tailing as shown in Table 3, but, under the effect of different quality concentration suspension, composite modified bentonite all is better than unmodified bentonite.
Claims (7)
1. a composite modified bentonite, is characterized in that adopting shitosan carry out load and make the modified alta-mud that passes through the ethylenediamine chelating.
2. composite modified bentonite according to claim 1, it is characterized in that: described shitosan, ethylenediamine, bentonitic mass/volume/mass ratio are 1～2g:1～4mL:5～15g.
3. the preparation method of composite modified bentonite according to claim 1 is characterized in that comprising the following steps:
<1 > get sodium bentonite and add the water stirring, be made into 10% suspension;
<2 > in 60～80 ℃ of water-baths, to step<1 > suspension in slowly add the pure ethylenediamine of analysis of 1～4mL, the limit edged stirs;
<3 > take in the acetum that 1～2g shitosan is dissolved in mass concentration 2%, be made into the chitosan solution of mass concentration 1～2%, stirring is dissolved fully to transparent clarification shitosan, then lentamente chitosan solution is added drop-wise to step<2 > mixed solution in, the loading process of shitosan carries out 2h in 80 ℃ of water-baths; Be cooled to again room temperature, wash 5 times after suction filtration, by gained filter cake heat drying in 60 ℃ of baking ovens, grind, cross 200 mesh sieves, obtain composite modified bentonite.
4. the described composite modified bentonite of claim 1 application aspect heavy metal in fixing mine tailing.
5. application according to claim 4, it is characterized in that: described heavy metal is zinc.
6. application according to claim 4 is characterized in that using by following operating procedure:
<1 > immobilization of mine tailing is processed
Composite modified bentonite is added in the 5mL deionized water, be made into the suspension of mass concentration 2～50%, evenly be added drop-wise to 50g mine tailing surface, place ventilation 48h, until suspension volatilizes;
<2 > reaction
Add deionized water by mass volume ratio 1:10 in the mine tailing after immobilization, regulate pH to 4, gained mineral water mixture is put to 200rpm/min concussion 12h on the isothermal vibration device.
7. application according to claim 6 characterized by further comprising following operating procedure:
<3 > measurement of heavy metal zinc in mine tailing
From step<2 > the mineral water mixture sample, centrifugal mistake 0.45 μ m filter membrane, utilize inductive coupling plasma emission spectrograph to measure the content of zinc in deionized water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109233859A (en) * | 2018-10-29 | 2019-01-18 | 云南圣清环保科技有限公司 | A kind of porous sustained-release composite passivant and the preparation method and application thereof for heavy metal-polluted soil passivation |
| CN111992258A (en) * | 2020-09-04 | 2020-11-27 | 广西大学 | Method for treating heavy metal pollution in sulfide ore tailings |
| CN112608078A (en) * | 2020-11-30 | 2021-04-06 | 深圳景源达建设集团有限公司 | Adhesive for wall tiling, preparation method thereof and wall tiling method adopting adhesive |
| CN115634668A (en) * | 2022-10-31 | 2023-01-24 | 同济大学 | Preparation and use methods of sodium bentonite-loaded chitosan heavy metal stabilizing agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233859A (en) * | 2018-10-29 | 2019-01-18 | 云南圣清环保科技有限公司 | A kind of porous sustained-release composite passivant and the preparation method and application thereof for heavy metal-polluted soil passivation |
| CN111992258A (en) * | 2020-09-04 | 2020-11-27 | 广西大学 | Method for treating heavy metal pollution in sulfide ore tailings |
| CN111992258B (en) * | 2020-09-04 | 2023-03-21 | 广西大学 | Method for treating heavy metal pollution in sulfide ore tailings |
| CN112608078A (en) * | 2020-11-30 | 2021-04-06 | 深圳景源达建设集团有限公司 | Adhesive for wall tiling, preparation method thereof and wall tiling method adopting adhesive |
| CN115634668A (en) * | 2022-10-31 | 2023-01-24 | 同济大学 | Preparation and use methods of sodium bentonite-loaded chitosan heavy metal stabilizing agent |
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