CN103464113B - Composite modified bentonite and its preparation method and application - Google Patents
Composite modified bentonite and its preparation method and application Download PDFInfo
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- CN103464113B CN103464113B CN201310431703.5A CN201310431703A CN103464113B CN 103464113 B CN103464113 B CN 103464113B CN 201310431703 A CN201310431703 A CN 201310431703A CN 103464113 B CN103464113 B CN 103464113B
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Abstract
The invention discloses a kind of composite modified bentonite, adopt shitosan carry out load to the modified alta-mud through ethylenediamine chelating and make.This composite modified bentonite can be used as heavy metal compound fixative, and be applied to the pollution control of mine tailing Leaching of Heavy Metals, the fixed capacity of heavy metal is large, crystallized ability is strong.Experiment proves, uses composite modified bentonite process mine tailing of the present invention, the leaching content of zinc in mine tailing not only can be made significantly to reduce (57 ~ 83%), and have good adsorption effect (62 ~ 97%) to the zinc in tailing leaching liquid.Meanwhile, preparation technology of the present invention is simple, with low cost, mild condition, is suitable for mining area tailings pollution and administers.
Description
Technical field
The invention belongs to modified alta-mud technical field, particularly relate to a kind of composite modified bentonite and its preparation method and application.
Background technology
China has the mineral resources compared with horn of plenty, and annual mining all produces along with a large amount of mine tailings.Under acid precipitation condition, heavy metal (as zinc, manganese etc.) is easier to be leached 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 to having a strong impact on, harm humans is healthy.Therefore, find effective ways reply mining area mine tailing heavy metal pollution to have great significance.
The method of current control 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, heavy metal fixative is used to be one of important control method.This method can suppress Leaching of Heavy Metals from source, and cost is lower, convenient and easy, can meet the requirement of administering heavy metals mining area and polluting very well, guarantee that its surrounding enviroment ecosystem is not contaminated.
The clay mineral of bentonite to be a kind of with montmorillonite be main component, at China's rich reserves, cheap.Modified alta-mud as Adsorption of Organic agent and containing heavy metal waste water treating agent in report more.But most of modifier price is higher, and treatment effect comparatively original soil improve little, so find convenient, efficient, economic novel heavy metal fixative to seem 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 heavy metal compound fixative, be applied to the pollution control of mine tailing Leaching of Heavy Metals, the fixed capacity of heavy metal is large, crystallized ability is strong.
For solving the problems of the technologies described above, the present invention by the following technical solutions: composite modified bentonite, adopt shitosan load is carried out to the modified alta-mud through ethylenediamine chelating and makes.
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> gets sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 60 ~ 80 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 1 ~ 4mL in the suspension of step <1>, and limit edged stirs;
<3> takes 1 ~ 2g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 1 ~ 2%, stirring makes shitosan dissolve fully to transparent clarification, then be added drop-wise in the mixed solution of step <2> by chitosan solution lentamente, the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
The application of above-mentioned composite modified bentonite in fixing mine tailing in heavy metal.
Heavy metal is zinc.
Above-mentioned application, uses by following operating procedure:
The immobilization process of <1> mine tailing
Composite modified bentonite is added in 5mL deionized water, be made into the suspension of mass concentration 2 ~ 50%, be evenly added drop-wise to 50g mine tailing surface, place ventilation 48h, until suspension volatilizes;
<2> reacts
In the mine tailing after immobilization, add deionized water by mass volume ratio 1:10, regulate pH to 4, gained mineral water mixture is put 200rpm/min on isothermal vibration device and shake 12h.
Apply according to claim 6, also comprise following operating procedure:
The measurement of heavy metal zinc in <3> mine tailing
Sample from the mineral water mixture of step <2>, centrifugal mistake 0.45 μm of filter membrane, utilize inductive coupling plasma emission spectrograph to measure the content of zinc in deionized water.The leaching content of zinc reduces percentage and calculates as follows:
Wherein, the reduction degree of L-zinc leaching content, X
before fixing-zinc leaching content in mine tailing when not adding fixative, X
after fixingzinc leaching content in mine tailing after-interpolation fixative.
The problem of excellent heavy metal fixative is lacked for current mine tailing Heavy Metal Pollution Control, inventor with the cheap and bentonite of rich reserves for raw material, with heavy metal chelant ethylenediamine and environmentally friendly natural polysaccharide shitosan for modifier, make a heavy metal species composite solid and determined agent---composite modified bentonite.Because ethylenediamine enters between bentonite bed, increase original soil interlamellar spacing, and utilize shitosan and bentonitic characterization of adsorption, by chitosan loaded on bentonite surface, both the secondary environmental pollution being used alone a large amount of ethylenediamine modifications and may causing had been overcome, can overcome again the problem being used alone the cost increase that shitosan brings, both use the effect of fixing heavy metal more excellent jointly.Experiment proves, uses composite modified bentonite process mine tailing of the present invention, the leaching content of zinc in mine tailing can be made significantly to reduce (57 ~ 83%).Meanwhile, preparation technology of the present invention is simple, with low cost, mild condition, is suitable for mining area tailings pollution and administers.
Detailed description of the invention
Embodiment 1
<1> gets 5g sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 80 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 4mL in the suspension of step <1>, and limit edged stirs;
<3> takes 2g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 2%, stirring makes shitosan dissolve fully to transparent clarification, then lentamente chitosan solution is added drop-wise in the mixed solution of step <2>, half an hour drips off, and the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
Embodiment 2
<1> gets 15g sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 60 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 1mL in the suspension of step <1>, and limit edged stirs;
<3> takes 1g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 1%, stirring makes shitosan dissolve fully to transparent clarification, then lentamente chitosan solution is added drop-wise in the mixed solution of step <2>, half an hour drips off, and the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
Embodiment 3
<1> gets 10g sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 60 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 4mL in the suspension of step <1>, and limit edged stirs;
<3> takes 2g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 2%, stirring makes shitosan dissolve fully to transparent clarification, then lentamente chitosan solution is added drop-wise in the mixed solution of step <2>, half an hour drips off, and the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
Embodiment 4
<1> gets 10g sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 70 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 3mL in the suspension of step <1>, and limit edged stirs;
<3> takes 1.5g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 1.5%, stirring makes shitosan dissolve fully to transparent clarification, then lentamente chitosan solution is added drop-wise in the mixed solution of step <2>, half an hour drips off, and the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
The adsorption applications of zinc in application examples 1 pair of tailing leaching liquid
To soak the tailing leaching liquid of 30 days by deionized water for working solution, 50mL working solution is measured in 100mL conical flask with 50mL graduated cylinder, take 0.05,0.1,0.2, the composite modified bentonite of 0.3g embodiment 2 and unmodified bentonite add in above-mentioned working solution, pH is regulated to be that 5.6,200r/min adsorbs 150min.Centrifugal rear mistake 0.45 μm of filter membrane, measures 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, when bentonite dosage is in low concentration, the effect of composite modified bentonite will obviously be better than unmodified bentonite.
Application examples 2
Somewhere mill tailings, after testing, wherein the content of heavy metal element zinc is the highest, and content is 3555m
g/ k
g.The composite modified bentonite of embodiment 3 is used to process by following operating procedure:
The immobilization process of <1> mine tailing
Unmodified bentonite and composite modified bentonite are added in 5mL deionized water, is made into the suspension of mass concentration 2 ~ 50%, be evenly added drop-wise to 50g mine tailing surface, place ventilation 48h, until suspension volatilizes;
<2> reacts
In the mine tailing after immobilization, add deionized water by mass volume ratio 1:10, regulate pH to 4, gained mineral water mixture is put 200rpm/min on isothermal vibration device and shake 12h.
The measurement of heavy metal zinc in <3> mine tailing
Sample from the mineral water mixture of step <2>, centrifugal mistake 0.45 μm of filter membrane, utilize inductive coupling plasma emission spectrograph to measure the content of zinc in deionized water.
The results are shown in Table 2.
The result of heavy metal zinc in mine tailing fixed by table 2
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 is all better than unmodified bentonite.
The application that in application examples 3 pairs of mine tailings, zinc is fixing
The composite modified bentonite of embodiment 4 and unmodified bentonite 0.1g, 0.5g, 1.5g, 2g, 2.5g are added in 5mL deionized water, be made into the suspension of 2%, 10%, 30%, 40%, 50% successively, evenly be added drop-wise to 50g mine tailing surface respectively, 48h is placed at shady and cool ventilation place, by regulate pH be 4 deionized water (simulation acidity larger acid rain) 500mL join in immobilized mine tailing, put into oscillator with the speed of 200r/min concussion 12h, and keep moisture, regulated pH that pH is remained unchanged every one hour.After 12h, 0.45 μm of filter membrane is crossed in centrifugation, measures zinc concentration in leachate.
The results are shown in Table 3.
The result of heavy metal zinc in mine tailing fixed by table 3
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 is all better than unmodified bentonite.
Claims (7)
1. a composite modified bentonite, is characterized in that adopting shitosan carry out load to the modified alta-mud through ethylenediamine chelating and make, specifically prepares according to the following steps:
<1> gets sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 60 ~ 80 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 1 ~ 4mL in the suspension of step <1>, and limit edged stirs;
<3> takes 1 ~ 2g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 1 ~ 2%, stirring makes shitosan dissolve fully to transparent clarification, then be added drop-wise in the mixed solution of step <2> by chitosan solution lentamente, the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
2. composite modified bentonite according to claim 1, 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> gets sodium bentonite and to add water stirring, is made into the suspension of 10%;
<2>, in 60 ~ 80 DEG C of water-baths, slowly adds the pure ethylenediamine of analysis of 1 ~ 4mL in the suspension of step <1>, and limit edged stirs;
<3> takes 1 ~ 2g shitosan and is dissolved in the acetum of mass concentration 2%, be made into the chitosan solution of mass concentration 1 ~ 2%, stirring makes shitosan dissolve fully to transparent clarification, then be added drop-wise in the mixed solution of step <2> by chitosan solution lentamente, the loading process of shitosan carries out 2h in 80 DEG C of water-baths; Be cooled to room temperature again, suction filtration after washing 5 times, by gained filter cake heat drying in 60 DEG C of baking ovens, grinding, crosses 200 mesh sieves, obtains composite modified bentonite.
4. the application of composite modified bentonite described in claim 1 in fixing mine tailing in heavy metal.
5. apply according to claim 4, it is characterized in that: described heavy metal is zinc.
6. apply according to claim 4, it is characterized in that using by following operating procedure:
The immobilization process of <1> mine tailing
Composite modified bentonite is added in 5mL deionized water, be made into the suspension of mass concentration 2 ~ 50%, be evenly added drop-wise to 50g mine tailing surface, place ventilation 48h, until suspension volatilizes;
<2> reacts
In the mine tailing after immobilization, add deionized water by mass volume ratio 1g:10mL, regulate pH to 4, gained mineral water mixture is put 200rpm/min on isothermal vibration device and shake 12h.
7. apply according to claim 6, characterized by further comprising following operating procedure:
The measurement of heavy metal zinc in <3> mine tailing
Sample from the mineral water mixture of step <2>, centrifugal mistake 0.45 μm of filter membrane, utilize inductive coupling plasma emission spectrograph to measure the content of zinc in deionized water.
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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 |
| 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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