CN102417214B - Method for adsorbing heavy metals by using three-dimensional compound consisting of graphene sheet and magnetotactic bacteria - Google Patents
Method for adsorbing heavy metals by using three-dimensional compound consisting of graphene sheet and magnetotactic bacteria Download PDFInfo
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- CN102417214B CN102417214B CN 201110322406 CN201110322406A CN102417214B CN 102417214 B CN102417214 B CN 102417214B CN 201110322406 CN201110322406 CN 201110322406 CN 201110322406 A CN201110322406 A CN 201110322406A CN 102417214 B CN102417214 B CN 102417214B
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- magnetotactic bacteria
- graphene film
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Abstract
The invention discloses a method for adsorbing heavy metals by using a three-dimensional compound consisting of a graphene sheet and magnetotactic bacteria. The method comprises the following steps of: fully mixing the graphene sheet and the magnetotactic bacteria in a liquid phase system to form a graphene sheet-magnetotactic bacteria three-dimensional compound; adding the graphene sheet-magnetotactic bacteria three-dimensional compound into sewage containing heavy metal ions; fully mixing to reach adsorption balance; and separating the graphene sheet-magnetotactic bacteria three-dimensional compound out by using an external magnetic field to realize the purification of sewage. The method has the advantages of simple process, capability of simultaneously treating sewage containing high-concentration complex heavy ion components such as Au<3+>, Fe<3+>, Ni<2+>, Cu<2+>, Pb<2+>, Cr<2+> and the like at the removing rate over 90 percent, recycling of the graphene sheet-magnetotactic bacteria three-dimensional compound through a magnetic field, low cost, environmental friendliness and no secondary pollution.
Description
Technical field
The present invention relates to a kind for the treatment of process that contains heavy metal ion sewage, relate in particular to a kind of method of utilizing graphene film and magnetotactic bacteria three-dimensional composite adsorption cleaning heavy metal, belong to purification of water quality and field of environment protection.
Background technology
Along with developing rapidly of China's industrial or agricultural, the quantity discharged of heavy metal ion-containing waste water is increases trend year by year, and all kinds of heavy metal in waste water content are constantly increasing on the one hand, and the heavy metal kind also becomes increasingly sophisticated simultaneously.Consider on the other hand chronicity and the seriousness of the harm that heavy metal causes human body and environment, country is also more and more stricter to the harmless treatment standard of heavy metal-containing waste water.Therefore, how economical, remove heavy metal ions in wastewater efficiently and become current very urgent task.
Traditional heavy metal treatment process is because its processing efficiency is lower, and expense is high, and the processing problem is single, causes easily that again the shortcoming such as secondary pollution eliminated by new treatment process just gradually.
For the waste water that comprises complicated heavy metal ion, the integrated conduct method that multiple purification techniques combines comes into one's own just day by day.The patent of invention of publication number CN101973620A proposes a kind of method of utilizing graphene oxide sheet to remove heavy metal ion in the water, although it can realize the adsorption cleaning to some heavy metal ion, but have adsorbable heavy metal ion kind, limited amount, graphene film reclaims the shortcoming of inconvenience after processing.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals, it can be realized containing the adsorption cleaning of contents of many kinds of heavy metal ion sewage, and technique is efficient, quick, simple, pollution-free, thereby has overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of method of utilizing graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals, it is characterized in that, the method is fully mixed in liquid-phase system with magnetotactic bacteria for getting graphene film, form graphene film-magnetotactic bacteria three-dimensional composite, then this graphene film-magnetotactic bacteria three-dimensional composite is added and contain in the sewage of heavy metal ion, after fully mixing reaches adsorption equilibrium, go out graphene film-magnetotactic bacteria three-dimensional composite to add magnetic field separation again, realize the purification to sewage;
Described heavy metal ion is selected from Au at least
3+, Fe
3+, Ni
2+, Cu
2+, Cr
2+And Pb
2+In any one or two or more.
Further, the concentration of described heavy metal ion can be 10mg/L-150 mg/L.
The method comprises the steps:
A, accompany by continue to stir and/or the condition of vibration under, get graphene film and fully mix in aqueous phase system with magnetotactic bacteria, formation graphene film-magnetotactic bacteria three-dimensional composite solution;
B, graphene film-magnetotactic bacteria three-dimensional composite solution added contain in the sewage of heavy metal ion, at room temperature continue to stir and/or vibration, until the hybrid reaction system that forms reaches the adsorption equilibrium state, again this hybrid reaction system is left standstill;
C, go out graphene film-magnetotactic bacteria three-dimensional composite to add magnetic field separation, realize the purification to sewage.
Preferably, described graphene film is any one in redox graphene sheet and the modification rear oxidation graphene film or two or more after graphene oxide sheet, redox graphene sheet, the modification;
After the modification graphene film surface active groups be selected from least in carboxyl, epoxy group(ing), hydroxyl, sulfydryl, amino, polyoxyethylene glycol and the tween any one or two or more.
Described magnetotactic bacteria be selected from least the mixed bacterial of enrichment from the mud of Taihu Lake and among the magnetic spirillum AMB-1 any one or two or more.
The mass percent of contained graphene film is 1%-30% in described graphene film-magnetotactic bacteria three-dimensional composite.
The concentration of contained graphene film-magnetotactic bacteria three-dimensional composite is 1 g/L-5g/L in described graphene film-magnetotactic bacteria three-dimensional composite solution.
More preferred, the method also can comprise the steps:
D, heavy metal ion desorption on graphene film-magnetotactic bacteria three-dimensional composite is attached then adds graphene film-magnetotactic bacteria three-dimensional composite in the sewage that contains heavy metal ion the operation of repeating step b-c again.
The method of utilizing graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metal Ions that the present invention proposes is a kind of novel method that is suitable for processing complicated effluent containing heavy metal ions.Graphene film and magnetotactic bacteria all have preferably heavy metal adsorption, and graphene film can fully contact with heavy metal ions in sewage and adsorb with its huge specific surface area, abundant surface functional group advantage.Magnetotactic bacteria fully disperses thalline by compound with graphene film, thereby more is conducive to the enrichment of heavy metal ions in sewage outside born of the same parents, precipitation, absorption or complexing.Magnetotactic bacteria adsorbs different metal ions from graphene film by the physics and chemistry mode, be suitable for processing the sewage that contains contents of many kinds of heavy metal ion, and handle the graphene film of sewage and magnetotactic bacteria three-dimensional composite and can reclaim by magnetic field and be reused.
With prior art, for example only compare with the sewage water treatment method of graphene film or magnetotactic bacteria single component, the characteristics such as the present invention is simple except having, green non-pollution, also have and once can process contents of many kinds of heavy metal ion, process the heavy metal ion kind many, clearance 90% with first-class advantage; Simultaneously the present invention can also effectively process some precious metals, and such as platinum, gold etc., and graphene film-magnetotactic bacteria three-dimensional composite also can reclaim and reuse by magnetic field, and is with low cost.
Embodiment
For shortcomings and deficiencies of the prior art, this case contriver has proposed to utilize the method for graphene film and magnetotactic bacteria three-dimensional composite adsorbing heavy metal ions in sewage through studying for a long period of time and putting into practice, and comprises the following steps:
(1) will in liquid phase, at room temperature fully mix with the magnetotactic bacteria concentrated solution by homodisperse graphene film, form three-dimensional composite.
(2) the three-dimensional composite solution that the first step is obtained is added in the sewage that contains contents of many kinds of heavy metal ion, by shaking up, leaves standstill, and makes to reach adsorption equilibrium.
(3) collect graphene film and the magnetotactic bacteria three-dimensional composite that absorption has various heavy metal ion, detect the content of each heavy metal ion in the sewage after treatment.
After the optional autoxidation graphene film of aforementioned graphene film, redox graphene sheet, modification rear oxidation Graphene and the modification in the redox graphene any one or two or more, the graphene film surface group is any one or a few in carboxyl, epoxy group(ing), hydroxyl, sulfydryl, amino, polyoxyethylene glycol, the tween.
Aforementioned magnetotactic bacteria comprises magnetotactic bacteria and the reference culture of enrichment from the mud of Taihu Lake: any one among the magnetic spirillum AMB-1 (Magnetospirillum sp.AMB-l) or two kinds.
In the abovementioned steps (1), that the magnetotactic bacteria bacterium liquid of centrifugal concentrating is being joined in the graphene film dispersion liquid of different concns under constantly stirring, the mass percent that makes graphene film finally account for three-dimensional composite is 1%-30%, and the final concentration that makes mixture is 1 g/L-5g/L.
Aforementioned heavy metal ion is Au
3+, Fe
3+, Ni
2+, Cu
2+, Pb
2+, Cr
2+In any one or a few, the concentration of heavy metal ion scope is from 10mg/L-150 mg/L.
Adopt graphene film and magnetotactic bacteria to form graphene film and magnetotactic bacteria three-dimensional composite by the layer by layer mutual coupling of Adsorption Phase in solution of physics and chemistry suction type among the present invention, again this three-dimensional composite solution is joined in the sewage that contains contents of many kinds of heavy metal ion, by shaking up, leave standstill, make and reach adsorption equilibrium, collect three-dimensional composite with magnetic field again, and the three-dimensional composite of collecting by the heavy metal ion desorption is attached can recycle.
Can process polytype heavy metal ion simultaneously by the present invention, and clearance reaches more than 90% all.
Below in conjunction with some preferred embodiments technical scheme of the present invention is described further.
Embodiment 1
The enrichment culture of magnetotactic bacteria in the mud of Taihu Lake: get top layer, Taihu Lake mud and wash through physiological saline, remove supernatant behind the gravity settling, stay precipitation to add enrichment medium, the static cultivation of room temperature 30 days, during changed one time nutrient solution every three days.
Substratum: NaNO
3250 mg/L, CH
3COONa 200 mg/L, HOOCCH
2CH
2COONa 1000 mg/L, Quinate iron 2 ml/L, ZnSO
450 mg/L, MnSO
450 mg/L, MgSO
47H
2O 50 mg/L, Vit.B
1250 mg/L, Sodium thioglycollate 100 mg/L.
Magnetotactic bacteria after the enrichment adopts patent two-way device for collecting magnetotactic bacteria (publication number is the device of mentioning among CN 101735937 A) to collect.Be magnetotactic bacteria more than 90% in little aerobic bacteria that method is collected thus, get this enrichment bacterium liquid and Graphene compound.
Get the magnetotactic bacteria of enrichment in the mud of Taihu Lake and magnetic spirillum AMB-1 (
MagnetospirillumSp. Strain AMB-l, available from ATCC, bacterial classification number: ATCC700264) the concentrated bacterium liquid 495mg of mixed bacterium, under room temperature constantly stirs, slowly join in the graphene oxide sheet and redox graphene mixing solutions of 100ml, 0.05mg/ml, after adding, continue to stir 30min, make fully to be mixed into three-dimensional composite, again the three-dimensional composite solution of making is joined 1L, contains Au
3+, Fe
3+, Ni
2+, Cu
2+, Pb
2+, Cr
2+Each ionic concn is in the sewage of 10mg/L, and stirring at room leaves standstill 30min after processing 1h, collect mixture with magnetic field after, the sewage of getting after the processing detects each heavy metal ion content with atomic absorption spectrum, finds that clearance can both reach more than 99.5%.
Embodiment 2
Get the concentrated bacterium liquid 450mg of magnetotactic bacteria of enrichment in the mud of aforementioned Taihu Lake, under room temperature constantly stirs, slowly join 100ml, in the redox graphene sheet solution of 0. 5mg/ml, after adding, continue to stir 30min, make fully to be mixed into three-dimensional composite.The three-dimensional composite solution of making is joined 1L, contain Fe
3+, Ni
2+, Cu
2+Each ionic concn is in the sewage of 50mg/L, and stirring at room leaves standstill 30min after processing 1h, collect mixture with magnetic field after, the sewage of getting after the processing detects each heavy metal ion content with atomic absorption spectrum, finds Fe
3+The clearance of ion is 98.7%, Ni
2+The clearance of ion is 99.3%, Cu
2+The clearance of ion is 97.4%.
Embodiment 3
Get the magnetotactic bacteria of enrichment in the mud of aforementioned Taihu Lake and the concentrated bacterium liquid 350mg of magnetic spirillum AMB-1 mixed bacterium, under room temperature constantly stirs, slowly join 100ml, 1.5mg/ml graphene oxide sheet solution in, after adding, continue to stir 30min, make fully to be mixed into three-dimensional composite, again the three-dimensional composite solution of making is joined 1L, contain Au
3+Ionic concn is in the sewage of 150mg/L, and stirring at room leaves standstill 30min after processing 1h, collect mixture with magnetic field after, the sewage of getting after the processing detects Au with atomic absorption spectrum
3+Ion content is found Au
3+The ion remaval rate can reach 99%.
Embodiment 4
Get the magnetotactic bacteria of enrichment in the mud of aforementioned Taihu Lake and the concentrated bacterium liquid 400mg of magnetic spirillum AMB-1 mixed bacterium, under room temperature constantly stirs, slowly join 100ml, in the graphene oxide sheet solution of 1mg/ml, after adding, continue to stir 30min, make fully to be mixed into three-dimensional composite.The three-dimensional composite solution of making is joined 1L, contain Au
3+, Pb
2+, Cr
2+Each ionic concn is in the sewage of 70mg/L, and stirring at room leaves standstill 30min after processing 1h, collect mixture with magnetic field after, the sewage of getting after the processing detects each heavy metal ion content with atomic absorption spectrum, finds Au
3+The clearance of ion is 90.7%, Pb
2+The clearance of ion is 91.3%, Cr
2+The clearance of ion is 90.4%.
Embodiment 5
Get the magnetotactic bacteria of enrichment in the mud of aforementioned Taihu Lake and the concentrated bacterium liquid 350mg of magnetic spirillum AMB-1 mixed bacterium, under room temperature constantly stirs, slowly join 100ml, 1.5mg/ml modification rear oxidation graphene film and modification after in the redox graphene mixing solutions, after adding, continue to stir 30min, make fully to be mixed into three-dimensional composite.The three-dimensional composite solution of making is joined 1L, contain Au
3+, Fe
3+, Ni
2+, Cu
2+, Pb
2+, Cr
2+Each ionic concn is in the sewage of 10mg/L, and stirring at room leaves standstill 30min after processing 1h, collect mixture with magnetic field after, the sewage of getting after the processing detects each heavy metal ion content with atomic absorption spectrum, finds to remove and can both reach more than 99%.
Should be understood that, the present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, the above embodiment of the present invention can only be thought can not limit the present invention to explanation of the present invention, claims have been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore in the implication suitable with claims of the present invention and any change in the scope, all should think to be included in the scope of claims.
Claims (6)
1. method of utilizing graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals, it is characterized in that, the method is: get graphene film and fully mix in liquid-phase system with magnetotactic bacteria, form graphene film-magnetotactic bacteria three-dimensional composite, then this graphene film-magnetotactic bacteria three-dimensional composite is added and contain in the sewage of heavy metal ion, after fully mixing reaches adsorption equilibrium, go out graphene film-magnetotactic bacteria three-dimensional composite to add magnetic field separation again, realize the purification to sewage;
Described heavy metal ion is selected from Au at least
3+, Fe
3+, Ni
2+, Cu
2+, Cr
2+And Pb
2+In any one or two or more.
2. utilize as claimed in claim 1 the method for graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals, it is characterized in that, the concentration of described heavy metal ion is 10mg/L-150mg/L.
3. utilize as claimed in claim 1 the method for graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals, it is characterized in that, the method comprises the steps:
A, accompany by continue to stir and/or the condition of vibration under, get graphene film and fully mix in aqueous phase system with magnetotactic bacteria, formation graphene film-magnetotactic bacteria three-dimensional composite solution;
B, graphene film-magnetotactic bacteria three-dimensional composite solution added contain in the sewage of heavy metal ion, at room temperature continue to stir and/or vibration, until the hybrid reaction system that forms reaches the adsorption equilibrium state, again this hybrid reaction system is left standstill;
C, go out graphene film-magnetotactic bacteria three-dimensional composite to add magnetic field separation, realize the purification to sewage.
4. as utilizing the method for graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals as described in claim 1 or 3, it is characterized in that, described graphene film is any one in the redox graphene sheet or two or more after redox graphene sheet and the modification after graphene oxide sheet, redox graphene sheet, the modification;
The active group that the graphene film surface has after the described modification be selected from least in carboxyl, epoxy group(ing), hydroxyl, sulfydryl, amino, polyoxyethylene glycol and the tween any one or two or more.
5. as utilizing the method for graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals as described in claim 1 or 3, it is characterized in that, the mass percent of contained total graphene film is 1%-30% in described graphene film-magnetotactic bacteria three-dimensional composite.
6. utilize as claimed in claim 3 the method for graphene film and magnetotactic bacteria three-dimensional composite Adsorption of Heavy Metals, it is characterized in that, the concentration of contained graphene film-magnetotactic bacteria three-dimensional composite is 1g/L-5g/L in described graphene film-magnetotactic bacteria three-dimensional composite solution.
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| CN 201110322406 CN102417214B (en) | 2011-10-21 | 2011-10-21 | Method for adsorbing heavy metals by using three-dimensional compound consisting of graphene sheet and magnetotactic bacteria |
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| CN102417214B true CN102417214B (en) | 2013-01-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103539253A (en) * | 2013-11-08 | 2014-01-29 | 青岛科技大学 | Preparation method of halotolerant bacteria composite carrier for salt-containing organic wastewater |
| CN104437364B (en) * | 2014-11-05 | 2017-10-20 | 中国科学院等离子体物理研究所 | A kind of regeneration method after the preparation method of graphene-supported nano zero-valence iron composite material and composite absorption pollutant |
| CN105036350A (en) * | 2015-06-04 | 2015-11-11 | 江苏维尔思环境工程有限公司 | Method for treating heavy metals in sewage by using phototactic bacteria |
| CN104986870B (en) * | 2015-07-10 | 2017-04-19 | 浙江大学 | Rice planting water heavy-metal pollution recycling treatment apparatus and control method |
| CN106423072A (en) * | 2016-09-21 | 2017-02-22 | 广东环境保护工程职业学院 | Graphene oxide-sulfhydryl compound composite capable of adsorbing heavy metal ions and preparation method of graphene oxide-sulfhydryl compound composite |
| CN106430633B (en) * | 2016-12-11 | 2018-09-18 | 湖南科技大学 | A kind of method that bacillus cereus removes heavy metal manganese in water removal |
| CN106865788B8 (en) * | 2017-04-09 | 2020-08-04 | 江苏峰业科技环保集团股份有限公司 | Industrial wastewater treatment method |
| CN107352656B (en) * | 2017-04-09 | 2021-04-20 | 刘慧� | Aluminum alloy industrial wastewater treatment method |
| CN107324616B (en) * | 2017-08-31 | 2018-07-24 | 衡水睿韬环保技术有限公司 | A kind for the treatment of process of heavy metal containing sewage |
| CN107913669A (en) * | 2017-11-27 | 2018-04-17 | 南京财经大学 | A kind of method that six heavy metal species in water environment are adsorbed based on magnetic graphene oxide |
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| JPH07328434A (en) * | 1994-06-03 | 1995-12-19 | Hokkaido Rehabili | Chromium adsorbent and treatment of waste chromium solution |
| GB0509307D0 (en) * | 2005-05-06 | 2005-06-15 | Isis Innovation | Derivatised carbon |
| CN101973620A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Method for removing heavy metal ions in water by using graphene oxide sheet |
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