CN102784624B - Preparation method and use of carbon coated magnetic adsorption material - Google Patents
Preparation method and use of carbon coated magnetic adsorption material Download PDFInfo
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- CN102784624B CN102784624B CN201210254084.2A CN201210254084A CN102784624B CN 102784624 B CN102784624 B CN 102784624B CN 201210254084 A CN201210254084 A CN 201210254084A CN 102784624 B CN102784624 B CN 102784624B
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Abstract
The invention discloses a preparation method of a carbon coated magnetic adsorption material. The preparation method which adopts a carbon source citric acid and nickel nitrate as raw materials comprises the following steps: dissolving the nickel nitrate and the carbon source in an aqueous ethanol solution at room temperature, wherein the mass ratio of the nickel nitrate to the carbon source is 1:3-10, and the volume ratio of ethanol to water of the aqueous ethanol solution is 1:1-5; uniformly stirring and mixing the solution; evaporating a solvent to obtain a solid mixture; grinding the mixture; and carbonizing through calcining the mixture in an inert gas environment to obtain the magnetic adsorption material having a carbon coating structure. The magnetic adsorption material prepared through the method has the advantages of carbon coating structure, uniform particle dimension distribution, large specific surface area, and realization of the rapid adsorption of pollutive heavy metal ions in sewage within a short period of time. Simultaneously the adsorption material has a magnetic property, so the adsorption material can realize quick separation and recovery under the action of an external magnetic field without the generation of secondary pollution. The method has the advantages of simple and safe operation, low cost, no environmental pollution, and according with practical production needs.
Description
One, technical field
The present invention relates to a kind of preparation method of functional material.Specifically, be a kind of preparation method of charcoal coated magnetic sorbing material and the application of this sorbing material polluted heavy metals ions in improvement sewage.
Two, background technology
Due to the exploitation of mankind's heavy metal, smelting, processing and business manufacturing activities increasing, cause heavy metal pollution of water body to increase the weight of, certain harm caused to ecological environment and human health.The waste water containing gold and the precious metal such as silver-colored can be produced in addition in industries such as chemical industry, plating, manufactures.Along with improving constantly of living standard, people are to environment, health, food-safety problem growing interest.Therefore, from healthy and economic angle, optionally removal, some precious metal of recovery and reuse are very important.
In existing technology, there is multiple method can realize the removal of heavy metal ion, as chemical precipitation method, ion floatation method, electrodeposit method, ion-exchange, electroosmose process, evaporation etc.These methods at cost, efficiency, complexity and cause secondary pollution aspect to there is certain limitation.And as a kind of simple, method that economy efficiently can remove polluted heavy metals ion in water, absorption method being paid close attention to widely in recent years, investigation and application.The adsorbent be developed and utilize has multiple, as active carbon, and silica gel, activated alumina, synthetic polymer and zeolite molecular sieve etc.But because these adsorbents are in stability, adsorption capacity, the deficiency of adsorptive selectivity aspect also various degrees, especially their complicated and loaded down with trivial details operating process such as separation, recovery, make it be subject to certain restrictions in the popularity of application.
Therefore, select a kind of simple and effective method preparing new material, make it have the good characteristics such as spheric granules micro-/ nano, porous, larger specific area, larger saturation magnetization, can quick separating under the effect of externally-applied magnetic field, and realize the recovery of sorbing material and precious metal ion and recycle.The deficiency in polluted heavy metals ion traditional treatment method can not only be overcome, and solve sorbing material, heavy metal recovery and highlight obvious advantage in utilizing.
Three, summary of the invention
The object of the present invention is to provide a kind of preparation method and application thereof of charcoal coated magnetic sorbing material.This charcoal coated magnetic sorbing material has good adsorption effect to the polluted heavy metals ion in polluted-water, and can realize the recovery of precious metal ion and sorbing material.
Realize technical scheme of the present invention:
Thinking of the present invention fully mixes in a solvent with nickel source and carbon source, obtains solid mixture, calcined in an inert atmosphere by solid mixture and obtain charcoal coated magnetic sorbing material after drying through grinding.
A preparation method for charcoal coated magnetic sorbing material, is characterized in that operating as follows:
1), by nickel nitrate and carbon source weigh 1:3 ~ 10 in mass ratio, joining volume ratio is in the ethanol water of 1:1 ~ 5, and at room temperature stirring and dissolving forms homogeneous phase solution;
2), by step 1) homogeneous phase solution that the obtains baking oven that is placed in 80 ~ 120 DEG C carries out drying, obtains solid mixture after drying through grinding;
3), by step 2) solid mixture that obtains is placed in tube furnace, in 550 ~ 850 DEG C of calcining 2 ~ 10h under atmosphere of inert gases, obtains charcoal coated magnetic sorbing material.
Described carbon source is selected from one or several in citric acid, glucose, oxalic acid, shitosan or urea.
Described atmosphere of inert gases is made up of argon gas or nitrogen or nitrogen-argon mixture gas.
Preferred calcination temperature 600 ~ 800 DEG C.
The purposes of charcoal coated magnetic sorbing material prepared by this method is as the application being separated, reclaiming adsorbent for heavy metal in waste water control.
The present invention adopts the carbon compounds such as cheap citric acid as carbon source, take nickel nitrate as magnetic source.Both are mixed into uniform stirring in ethanol water, after solvent evaporated grinding, then the calcination process carrying out gentleness just a step can obtain charcoal coated magnetic composite.This magnetic adsorptive material with charcoal clad structure prepared is as a kind of novel surrounding purifying functional material; within a short period of time can polluted heavy metals ion in absorption effluent; recycling and the recovery of precious metal sorbing material can be realized simultaneously; reduce costs; economical and effective and do not produce secondary pollution, for the production application expanding industrial scale provides certain Research foundation.
Effect of the present invention and advantage:
1, the magnetic adsorptive material that obtains of the inventive method, have charcoal clad structure, Stability Analysis of Structures, and specific area reaches 200m
2g
-1above.
2, this sorbing material has magnetic, thus under the effect of external magnetic field, just can realize quick separating, and not produce secondary pollution.
3, compared with existing synthesizing magnetic material technology, whole technical process preparation method is simple and safe, and cost is low, and productive rate is high, non-environmental-pollution.And adsorption fouling heavy metal ion just can reach adsorption equilibrium in 30 ~ 50min.
Four, accompanying drawing explanation
Figure l is the XRD figure of sample prepared by embodiment 3;
Fig. 2, Fig. 3 are SEM figure and the TEM figure of embodiment 3 products therefrom respectively; Wherein Fig. 2 is the overall picture of gained magnetic adsorptive material, and magnetic adsorptive material obtained as can be seen from Figure has equally distributed microballoon pattern; Fig. 3 is the high resolution structure feature of gained sorbing material respectively, has obvious charcoal clad structure, coating thickness 2-3nm from the known obtained magnetic adsorptive material of gained picture.
Fig. 4 is the N of embodiment 3 gained magnetic adsorptive material
2adsorb a desorption curve and graph of pore diameter distribution; Average pore size can be obtained by pore size distribution curve figure and be about 20nm.
Fig. 5 is that the magnetic material of embodiment 3 gained is to different heavy metal ion (Pb
2+and Cu
2+) adsorption curve figure; Adsorption process can be obtained in 30 ~ 50min, just can reach adsorption equilibrium from curve map, illustrate that the speed of obtained magnetic adsorbent adsorbing metal ions is fast, successful.
Five, detailed description of the invention
Below in conjunction with drawings and Examples, the present invention will be described further.
Embodiment 1
The preparation of charcoal coated magnetic sorbing material
Preparation process is as follows successively:
1), by 3.0g glucose and 1.0g nickel nitrate joining 80mL volume ratio is in the ethanol water of 1:1, forms homogeneous phase solution under magnetic stirring;
2), by step 1) homogeneous phase solution that obtains be heated to 105 DEG C make it dry solid mixture, then fully grind in mortar.
3), by step 2) solid mixture after grinding, in tube furnace, calcine 2h under 700 DEG C of argon atmospheres, obtain and there is the magnetic adsorptive material of charcoal clad structure.
Embodiment 2
Lead ion and copper ion experiment in the charcoal coated magnetic sorbing material absorption effluent be prepared into by embodiment 1
1) 3.197g plumbi nitras Pb (NO, is taken
3)
2solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1pb
2+standard liquid:
Take 7.6039g Gerhardite Cu (NO
3)
23H
2o solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1cu
2+standard liquid.
2) standard liquid that, removing step 1 is obtained is diluted to 20.0mgL respectively
-1the each 500mL of simulation sewage with for subsequent use:
3), lead ion and copper ion experiment in absorption effluent, experiment is carried out at ambient temperature, does not need the pH value regulating sewage, and adding the concentration being prepared into magnetic adsorptive material by embodiment 1 is 0.8gL
-1, start timing after being evenly spread to by adsorbent in sewage, whole adsorption process keeps stabilizing mechanical to stir, and samples under different adsorption time sections, and institute samples liquid after filtering must supernatant fluid filtrate, and filtrate is analyzed with atomic absorption spectrum.Analysis result is depicted as adsorption curve figure.
Embodiment 3
The preparation of charcoal coated magnetic sorbing material
Preparation process is as follows successively:
1), by 5.0g citric acid and 1.0g nickel nitrate joining 80mL volume ratio is in the ethanol water of 1:3, forms homogeneous phase solution under magnetic stirring;
2), by step 1) homogeneous phase solution that obtains be heated to 105 DEG C make it dry solid mixture, then fully grind in mortar.
3), by step 2) solid mixture after grinding, in tube furnace, calcine 2h under 600 DEG C of argon atmospheres, obtain and there is the magnetic adsorptive material of charcoal clad structure.
Embodiment 4
Lead ion and copper ion experiment in the charcoal coated magnetic sorbing material absorption effluent be prepared into by embodiment 3
1) 3.197g plumbi nitras Pb (NO, is taken
3)
2solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1pb
2+standard liquid:
Take 7.6039g Gerhardite Cu (NO
3)
23H
2o solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1cu
2+standard liquid.
2) standard liquid that, removing step 1 is obtained is diluted to 40.0mgL respectively
-1the each 500mL of simulation sewage with for subsequent use:
3), lead ion and copper ion experiment in absorption effluent, experiment is carried out at ambient temperature, does not need the pH value regulating sewage, and adding the concentration being prepared into magnetic adsorptive material by embodiment 7 is 0.8gL
-1, start timing after being evenly spread to by adsorbent in sewage, whole adsorption process keeps stabilizing mechanical to stir, and samples under different adsorption time sections, and institute samples liquid after filtering must supernatant fluid filtrate, and filtrate is analyzed with atomic absorption spectrum.Analysis result is depicted as adsorption curve figure.
Embodiment 5
The preparation of charcoal coated magnetic sorbing material
Preparation process is as follows successively:
1), by 7.5g oxalic acid and 1.0g nickel nitrate joining 100mL volume ratio is in the ethanol water of 1:4, forms homogeneous phase solution under magnetic stirring;
2), by step 1) homogeneous phase solution that obtains be heated to 110 DEG C make it dry solid mixture, then fully grind in mortar.
3), by step 2) solid mixture after grinding, in tube furnace, calcine 3h under 650 DEG C of argon atmospheres, obtain and there is the magnetic adsorptive material of charcoal clad structure.
Embodiment 6
Lead ion and copper ion experiment in the charcoal coated magnetic sorbing material absorption effluent be prepared into by embodiment 5
1) 3.197g plumbi nitras Pb (NO, is taken
3)
2solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1pb
2+standard liquid:
Take 7.6039g Gerhardite Cu (NO
3)
23H
2o solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1cu
2+standard liquid.
2) standard liquid that, removing step 1 is obtained is diluted to 50.0mgL respectively
-1the each 500mL of simulation sewage with for subsequent use:
3), lead ion and copper ion experiment in absorption effluent, experiment is carried out at ambient temperature, does not need the pH value regulating sewage, and adding the concentration being prepared into magnetic adsorptive material by embodiment 5 is 1.0gL
-1, start timing after being evenly spread to by adsorbent in sewage, whole adsorption process keeps stabilizing mechanical to stir, and samples under different adsorption time sections, and institute samples liquid after filtering must supernatant fluid filtrate, and filtrate is analyzed with atomic absorption spectrum.Analysis result is depicted as adsorption curve figure.
Embodiment 7
The preparation of charcoal coated magnetic sorbing material
Preparation process is as follows successively:
1), by 10.0g urea and 1.0g nickel nitrate joining 100mL volume ratio is in the ethanol water of 1:5, forms homogeneous phase solution under magnetic stirring;
2), by step 1) homogeneous phase solution that obtains be heated to 110 DEG C make it dry solid mixture, then fully grind in mortar.
3), by step 2) solid mixture after grinding, in tube furnace, calcine 4h under 800 DEG C of argon atmospheres, obtain and there is the magnetic adsorptive material of charcoal clad structure.
Embodiment 8
Lead ion and copper ion experiment in the charcoal coated magnetic sorbing material absorption effluent be prepared into by embodiment 7
1) 3.197g plumbi nitras Pb (NO, is taken
3)
2solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1pb
2+standard liquid:
Take 7.6039g Gerhardite Cu (NO
3)
23H
2o solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1cu
2+standard liquid.
2) standard liquid that, removing step 1 is obtained is diluted to 40.0mgL respectively
-1the each 500mL of simulation sewage with for subsequent use:
3), lead ion and copper ion experiment in absorption effluent, experiment is carried out at ambient temperature, does not need the pH value regulating sewage, and adding the concentration being prepared into magnetic adsorptive material by embodiment 7 is 1.0gL
-1, start timing after being evenly spread to by adsorbent in sewage, whole adsorption process keeps stabilizing mechanical to stir, and samples under different adsorption time sections, and institute samples liquid after filtering must supernatant fluid filtrate, and filtrate is analyzed with atomic absorption spectrum.Analysis result is depicted as adsorption curve figure.
Claims (1)
1. an application for charcoal coated magnetic sorbing material, is characterized in that:
The preparation process of charcoal coated magnetic sorbing material is as follows successively:
1), by 3.0g glucose and 1.0g nickel nitrate joining 80mL volume ratio is in the ethanol water of 1:1, forms homogeneous phase solution under magnetic stirring;
2), by step 1) homogeneous phase solution that obtains be heated to 105 DEG C make it dry solid mixture, then fully grind in mortar;
3), by step 2) solid mixture after grinding, in tube furnace, calcine 2h under 700 DEG C of argon atmospheres, obtain and there is the magnetic adsorptive material of charcoal clad structure;
Lead ion and copper ion in the charcoal coated magnetic sorbing material absorption effluent be prepared into by said method, step is as follows:
A) 3.197g plumbi nitras Pb (NO, is taken
3)
2solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1pb
2+standard liquid;
Take 7.6039g Gerhardite Cu (NO
3)
23H
2o solid distilled water is dissolved in the volumetric flask of 1000mL, and being mixed with concentration is 2gL
-1cu
2+standard liquid;
B) standard liquid that, removing step a is obtained is diluted to 20.0mgL respectively
-1the each 500mL of simulation sewage with for subsequent use;
C), lead ion and copper ion experiment in absorption effluent, experiment is carried out at ambient temperature, and do not need the pH value regulating sewage, adding by the above-mentioned concentration being prepared into magnetic adsorptive material is 0.8gL
-1, start timing after being evenly spread to by adsorbent in sewage, whole adsorption process keeps stabilizing mechanical to stir, and samples under different adsorption time sections, and institute samples liquid after filtering must supernatant fluid filtrate, and filtrate is analyzed with atomic absorption spectrum.
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| CN104941585B (en) * | 2015-05-27 | 2018-06-26 | 江苏大学 | It is a kind of rich in carboxyl simultaneously can magnetic recovery heavy metal absorbent preparation method |
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| CN106914219A (en) * | 2017-04-07 | 2017-07-04 | 安徽工业大学 | A kind of application of magnetic carbosphere Cr VI in waste water is removed |
| CN106925219A (en) * | 2017-04-20 | 2017-07-07 | 兰州交通大学 | A kind of preparation method of magnetic carbon composite adsorbing material |
| CN109309214B (en) * | 2017-07-28 | 2023-04-11 | 中国石油化工股份有限公司 | Preparation method of carbon-coated nickel nano composite material |
| CN107469829A (en) * | 2017-09-22 | 2017-12-15 | 常州大学 | A kind of preparation method of the compound wolframic acid iron catalyst of carbon |
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| CN110451507B (en) * | 2019-07-30 | 2021-07-30 | 深圳大学 | Preparation method of porous carbon material, supercapacitor electrode and supercapacitor |
| US11969713B2 (en) * | 2019-12-19 | 2024-04-30 | Northeastern University | Graphene-transition metal catalyst for hydrogen evolution reaction |
| CN113713761A (en) * | 2021-07-30 | 2021-11-30 | 安徽建筑大学 | Method for adsorbing and removing hexavalent chromium in wastewater and nickel-carbon composite material used by same |
| CN115925027B (en) * | 2023-03-10 | 2023-05-30 | 湖南国重环境科技有限责任公司 | Fermentation type antibiotic production wastewater pretreatment system |
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| CN101176915A (en) * | 2006-11-09 | 2008-05-14 | 南京大学 | Method for preparing nano metallic nickel granular material coating with carbon |
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