CN104190369A - Preparation method of heavy metal ion bio-adsorbent - Google Patents
Preparation method of heavy metal ion bio-adsorbent Download PDFInfo
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- CN104190369A CN104190369A CN201410395844.0A CN201410395844A CN104190369A CN 104190369 A CN104190369 A CN 104190369A CN 201410395844 A CN201410395844 A CN 201410395844A CN 104190369 A CN104190369 A CN 104190369A
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Abstract
The invention relates to a preparation method of a heavy metal ion bio-adsorbent, aiming at solving the problems of secondary pollution, low removal rate, high operating difficulty and high cost in the prior art. The preparation method comprises the steps of adding chitosan into an acetic acid liquid and stirring until the chitosan is dissolved to obtain a chitosan liquid; adding GPTMS into the chitosan liquid, stirring, carrying out ultrasonic treatment, adding activated silica gel, and stirring to carry out sol-gel process to obtain chitosan supported silica gel; immersing the chitosan supported silica gel in an alkaline liquid for ammonification culture, separating the chitosan supported silica gel subjected to ammonification culture from the alkaline liquid, washing the chitosan supported silica gel subjected to ammonification culture with water to be neutral, and airing in a vacuum environment to obtain the heavy metal ion bio-adsorbent; and the heavy metal ion bio-adsorbent can be used for solving the problems and can be used for low-concentration heavy metal waste water treatment.
Description
Technical field
The present invention relates to a kind of preparation method of heavy metal ion biological adsorption agent.
Background technology
In water, heavy metal pollution is society question of common concern, and it not only has a strong impact on people's health, and animals and plants and microorganism are also existed to serious potential ecology threat.Not vital movement institute is essential as lead, cadmium, manganese, copper, mercury etc. for most of heavy metal, but these pollutants of low dosage just can make organism metabolism get muddled, and induce an illness, even dead.The heavy metal ion of discharging with waste water even if concentration is little, also can accumulate in algae and bed mud, is adsorbed by the body surface of fish and shellfish, participates in food chain, in the time being enriched to higher concentration, can cause serious harm to people's health.
Chemical precipitation, distillation, plating, ion-exchange and film separates etc. that technology has been used to remove and reclaim the metal ion in waste water, but ubiquity secondary pollution, in the time that the concentration of heavy metal ion in waste water is lower, these technology removal efficiency are low or operating cost is higher.
Biological adsorption is a kind of emerging removal of heavy metal ions technology at present, more and more receives people's concern, and biological adsorption is exactly the absorption to heavy metal ion in water by organism and derivative thereof, reaches the object of heavy-metal ion removal.Can Adsorption of Heavy Metal Ions and the biomaterial of other pollutant be called biological adsorption agent.The removal that biological adsorption is heavy metal ions in wastewater provides a kind of economically viable technology, its raw material sources are extensive and cheap, can reach desirable treatment effect, biosorption technology has vast potential for future development in the industrial purification that is applied to heavy metal ions in wastewater.
CN201110127112.X discloses a kind of biomass adsorbent for heavy metal containing wastewater treatment and process for treating heavy-metal waste water, and described biomass adsorbent is dehydrated and then clayed into power and make by corchorus olitorius.The method that described heavy metal wastewater thereby is processed, is that described adsorbent is sprinkled in heavy metal wastewater thereby, then shakes heavy metal wastewater thereby.
Shitosan has the characteristic of a series of excellences, comprising: hydrophily, biocompatibility, nontoxic etc. are a kind of functional high-polymer biomaterials that extensive use is worth that has.In addition, in chitosan molecule, contain active amino, can carry out many chemical reactions, form multiple derivative.What is more important, amino can form coordination and metal ion is directly fixed on chitosan material with metal ion.In order to overcome, shitosan is acid-soluble, the shortcoming of bad mechanical strength, and the compound biological adsorption agent of preparation inorganic material support type chitin organic-inorganic is the focus that people study for the removal of heavy metals ion.
Silica gel is a kind of typical inorganic material, has that specific area is large, mechanical strength advantages of higher.Preparing silica gel support shitosan shaped material can effectively combine the functional of mechanical strength high silica gel and shitosan.
Be directed to this, proposed a kind of preparation method of heavy metal ion biological adsorption agent.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to have secondary pollution, removal efficiency is low, operation easier is large and cost is high problem, and a kind of preparation method of new heavy metal ion biological adsorption agent is provided.The method is for containing the processing of low concentration heavy metal water, has advantages of the secondary pollution of not existing, removal efficiency is high, operation easier is little and cost is low.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of preparation method of heavy metal ion biological adsorption agent, in acetum, add shitosan, stir so that shitosan is dissolved, obtain chitosan solution, then in described chitosan solution, add GPTMS, through stirring, after ultrasonic, add the silica gel activating and stir, carry out sol gel process, obtain the silica gel of support shitosan, the silica gel of described support shitosan is immersed in alkaline solution and carries out ammonification cultivation, from described alkaline solution, separate the silica gel of the support shitosan of cultivating through ammonification, water rinses to neutral, then in vacuum environment, dry, obtain heavy metal ion biological adsorption agent.
In technique scheme, preferably, described silica gel is spherical, at 80～150 DEG C, activates 0.2～2h, obtains the active silica gel of crossing.
In technique scheme, preferably, the weight ratio of shitosan and acetum is 1:99～3:100.
In technique scheme, preferably, the weight ratio of described GPTMS and chitosan solution is 0.5:100～1.5:100.
In technique scheme, preferably, in described chitosan solution, add GPTMS, after stirring 0.2～2h, ultrasonic 0.2～2h, then by the silica gel activating according to the weight ratio of chitosan solution be that 1:2.1～1:1.8 adds, after stirring, at 10～25 DEG C in culture dish 6～14h, realize sol gel process.
In technique scheme, preferably, described alkaline solution is NaOH solution, and pH is 13.0～13.8, and the weight ratio of the silica gel of support shitosan and NaOH solution is 1:4～1:2.
In technique scheme, preferably, the spherical silica gel of support shitosan is immersed in NaOH solution and carries out ammonification cultivation, leave standstill 10～25h, after separating the silica gel of the support shitosan of cultivating through ammonification sodium hydroxide solution, rinse to neutral by secondary deionized water, in vacuum environment, dry, vacuum is-0.09MPa～-0.1MPa.
GPTMS of the present invention is γ-glycidoxypropyltrimethoxy silane, and its molecular formula is:
In sol-gel process, after GPTMS adds, by acid catalyzed silane, from hydrolysis, original position produces silicon hydroxyl, on silane reagent, occur subsequently silicon hydroxyl from condensation.Meanwhile, the amino on shitosan chain adds on the epoxide group of silane reagent.These two kinds of polymerization processes make Silica Surface occur orderly self assembly cause covalency apply.Between oxygen atom in silicon hydroxyl, the polysiloxanes network of amino in chitosan molecule, hydroxyl, not condensation, form multiple hydrogen bonding effect.In addition, the cocondensation of the silicon hydroxyl on silane and Silica Surface silicon hydroxyl can improve as the adhesion between silica gel and the hybrid material of Zhi Zaiti.
Biological adsorption agent preparation method of the present invention is simple, cost is low, low-concentration heavy metal ions is adsorbed rapidly and efficiently, and desorption is high with recycling property, does not have secondary pollution, obtains good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
Silica gel is spherical, at 150 DEG C, activates 0.2h, obtains the active silica gel of crossing.In acetum, add shitosan, the weight ratio of shitosan and acetum is 3:100, stir so that shitosan is dissolved, obtain chitosan solution, then in described chitosan solution, add GPTMS, the weight ratio of GPTMS and chitosan solution is 1.5:100, through stirring 0.2h, after ultrasonic 0.2h, add the silica gel activating and stir, the silica gel activating according to the weight ratio of chitosan solution be 1:2.1, after stirring, at room temperature 14h in culture dish, carry out sol gel process, obtain the silica gel of support shitosan, the silica gel of described support shitosan is immersed in NaOH solution and carries out ammonification cultivation, the pH of NaOH solution is 13.8, the weight ratio of the silica gel of support shitosan and NaOH solution is 1:4.The spherical silica gel of support shitosan is immersed in NaOH solution and carries out ammonification cultivation, leave standstill 25h, after separating the silica gel of the support shitosan of cultivating through ammonification sodium hydroxide solution, rinse extremely neutral by secondary deionized water, in vacuum environment, dry, vacuum is-0.1MPa finally to obtain heavy metal ion biological adsorption agent.
Test adsorbent at the absorption behavior of processing in electroplating wastewater by column chromatography.Waste water is from the grand Electroplate Factory in Shandong, and the pH of waste water is 5～6, and the filter that is then 0.45mm with aperture carries out overanxious, measures Cu in waste water
2+initial concentration be 26.6mg/L.The biological adsorption agent of preparation is installed in the chromatographic column that internal diameter is 2.6cm (volume is 50mL).With the speed of 2mL/min, the waste water solution that contains metal ion is drawn in post with peristaltic pump, calculates the Cu in waste water
2+concentration is 3.19mg/L, Cu in waste water
2+removal efficiency reaches 88.8%, shows that this adsorbent has good removal Cu
2+ability.
[embodiment 2]
According to condition and step described in embodiment 1, silica gel is spherical, at 80 DEG C, activates 2h, obtains the active silica gel of crossing.In acetum, add shitosan, the weight ratio of shitosan and acetum is 1:99, stir so that shitosan is dissolved, obtain chitosan solution, then in described chitosan solution, add GPTMS, the weight ratio of GPTMS and chitosan solution is 0.5:100, through stirring 2h, after ultrasonic 2h, add the silica gel activating and stir, the silica gel activating according to the weight ratio of chitosan solution be 1:1.8, after stirring, at 15 DEG C in culture dish 6h, carry out sol gel process, obtain the silica gel of support shitosan, the silica gel of described support shitosan is immersed in NaOH solution and carries out ammonification cultivation, the pH of NaOH solution is 13, the weight ratio of the silica gel of support shitosan and NaOH solution is 1:2.The spherical silica gel of support shitosan is immersed in NaOH solution and carries out ammonification cultivation, leave standstill 10 h, after separating the silica gel of the support shitosan of cultivating through ammonification sodium hydroxide solution, rinse extremely neutral by secondary deionized water, in vacuum environment, dry, vacuum is-0.09MPa finally to obtain heavy metal ion biological adsorption agent.
Cu in waste water
2+removal efficiency reaches 87%.
[embodiment 3]
According to condition and step described in embodiment 1, silica gel is spherical, at 110 DEG C, activates 1h, obtains the active silica gel of crossing.In acetum, add shitosan, the weight ratio of shitosan and acetum is 1:49, stir so that shitosan is dissolved, obtain chitosan solution, then in described chitosan solution, add GPTMS, the weight ratio of GPTMS and chitosan solution is 1:100, through stirring 1h, after ultrasonic 1h, add the silica gel activating and stir, the silica gel activating according to the weight ratio of chitosan solution be 1:2, after stirring, at 15 DEG C in culture dish 12h, carry out sol gel process, obtain the silica gel of support shitosan, the silica gel of described support shitosan is immersed in NaOH solution and carries out ammonification cultivation, the pH of NaOH solution is 13.7, the weight ratio of the silica gel of support shitosan and NaOH solution is 1:3.The spherical silica gel of support shitosan is immersed in NaOH solution and carries out ammonification cultivation, leave standstill 18h, after separating the silica gel of the support shitosan of cultivating through ammonification sodium hydroxide solution, rinse extremely neutral by secondary deionized water, in vacuum environment, dry, vacuum is-0.095MPa finally to obtain heavy metal ion biological adsorption agent.
Cu in waste water
2+removal efficiency reaches 96.2%.
Claims (7)
1. the preparation method of a heavy metal ion biological adsorption agent, in acetum, add shitosan, stir so that shitosan is dissolved, obtain chitosan solution, then in described chitosan solution, add GPTMS, through stirring, after ultrasonic, add the silica gel activating and stir, carry out sol gel process, obtain the silica gel of support shitosan, the silica gel of described support shitosan is immersed in alkaline solution and carries out ammonification cultivation, from described alkaline solution, separate the silica gel of the support shitosan of cultivating through ammonification, water rinses to neutral, then in vacuum environment, dry, obtain heavy metal ion biological adsorption agent.
2. the preparation method of heavy metal ion biological adsorption agent according to claim 1, is characterized in that described silica gel is spherical, at 80～150 DEG C, activates 0.2～2h, obtains the active silica gel of crossing.
3. the preparation method of heavy metal ion biological adsorption agent according to claim 1, the weight ratio that it is characterized in that shitosan and acetum is 1:99～3:100.
4. the preparation method of heavy metal ion biological adsorption agent according to claim 1, the weight ratio that it is characterized in that described GPTMS and chitosan solution is 0.5:100～1.5:100.
5. the preparation method of heavy metal ion biological adsorption agent according to claim 1, it is characterized in that adding GPTMS in described chitosan solution, after stirring 0.2～2h, ultrasonic 0.2～2h, then by the silica gel activating according to the weight ratio of chitosan solution be that 1:2.1～1:1.8 adds, after stirring, at 10～25 DEG C in culture dish 6～14h, realize sol gel process.
6. the preparation method of heavy metal ion biological adsorption agent according to claim 1, is characterized in that described alkaline solution is NaOH solution, and pH is 13.0～13.8, and the weight ratio of the silica gel of support shitosan and NaOH solution is 1:4～1:2.
7. according to the preparation method of heavy metal ion biological adsorption agent described in claim 1,6, it is characterized in that the spherical silica gel of support shitosan to immerse in NaOH solution and carry out ammonification cultivation, leave standstill 10～25h, after separating the silica gel of the support shitosan of cultivating through ammonification sodium hydroxide solution, rinse extremely neutral by secondary deionized water, in vacuum environment, dry, vacuum is-0.09MPa～-0.1MPa.
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Cited By (8)
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| CN106053636A (en) * | 2016-05-25 | 2016-10-26 | 中南大学 | Method for detecting content of trace metal ions |
| CN107149925A (en) * | 2017-07-13 | 2017-09-12 | 韦卓林 | Heavy metal absorbent prepared by a kind of utilization bog moss and preparation method thereof |
| CN107159167A (en) * | 2017-07-13 | 2017-09-15 | 韦卓林 | Heavy metal absorbent prepared by a kind of utilization rice straw and preparation method thereof |
| CN107282019A (en) * | 2017-07-13 | 2017-10-24 | 韦卓林 | Heavy metal absorbent prepared by a kind of utilization cereal shell and preparation method thereof |
| CN107805280A (en) * | 2017-10-10 | 2018-03-16 | 湖北世厚耀榜纪田农业发展有限公司 | A kind of method that heavy metal is removed in the liver metallothionein from giant salamander |
| CN111748057A (en) * | 2020-07-09 | 2020-10-09 | 重庆工商大学 | Method for synthesizing gum arabic high polymer by composite initiation system |
| CN112473630A (en) * | 2020-11-13 | 2021-03-12 | 山东东岳化工有限公司 | Composite graphene chitosan aerogel and preparation method and application thereof |
| CN112551496A (en) * | 2020-12-07 | 2021-03-26 | 安徽辉隆中成科技有限公司 | Method and device for removing phosphoric acid impurities |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053636A (en) * | 2016-05-25 | 2016-10-26 | 中南大学 | Method for detecting content of trace metal ions |
| CN107149925A (en) * | 2017-07-13 | 2017-09-12 | 韦卓林 | Heavy metal absorbent prepared by a kind of utilization bog moss and preparation method thereof |
| CN107159167A (en) * | 2017-07-13 | 2017-09-15 | 韦卓林 | Heavy metal absorbent prepared by a kind of utilization rice straw and preparation method thereof |
| CN107282019A (en) * | 2017-07-13 | 2017-10-24 | 韦卓林 | Heavy metal absorbent prepared by a kind of utilization cereal shell and preparation method thereof |
| CN107805280A (en) * | 2017-10-10 | 2018-03-16 | 湖北世厚耀榜纪田农业发展有限公司 | A kind of method that heavy metal is removed in the liver metallothionein from giant salamander |
| CN111748057A (en) * | 2020-07-09 | 2020-10-09 | 重庆工商大学 | Method for synthesizing gum arabic high polymer by composite initiation system |
| CN112473630A (en) * | 2020-11-13 | 2021-03-12 | 山东东岳化工有限公司 | Composite graphene chitosan aerogel and preparation method and application thereof |
| CN112551496A (en) * | 2020-12-07 | 2021-03-26 | 安徽辉隆中成科技有限公司 | Method and device for removing phosphoric acid impurities |
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