CN102233259A - Adsorbent for removing heavy metal from water and preparation method of adsorbent - Google Patents
Adsorbent for removing heavy metal from water and preparation method of adsorbent Download PDFInfo
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- CN102233259A CN102233259A CN 201010161774 CN201010161774A CN102233259A CN 102233259 A CN102233259 A CN 102233259A CN 201010161774 CN201010161774 CN 201010161774 CN 201010161774 A CN201010161774 A CN 201010161774A CN 102233259 A CN102233259 A CN 102233259A
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Abstract
The invention discloses an adsorbent for removing heavy metal from water and a preparation method of the adsorbent, and belongs to the fields of water treatment technologies and application. The adsorbent for removing the heavy metal from the water comprises the following raw materials of a high polymer material, a metal oxide and a pore-forming agent. The prepared adsorbent has high heavy metal adsorption capacity and high adsorption speed and thoroughly removes the heavy metal from the water at high removal efficiency of over 95 percent.
Description
Invention field
The present invention relates to a kind of adsorbent of removing heavy metal in the water, specifically is granular sorbing material of a kind of macromolecular material fixing metal oxide and preparation technology thereof, belongs to water technology and application.
Background of invention
The develop rapidly of world today's industry has produced the waste water that contains heavy metal ion in a large number, because heavy metal ion reveals very high toxicity to organism surface, can produce heavy damage to receiving water body, so heavy metal pollution has become in the world today one of serious environmental problem.Heavy metal in the water body mainly comprises As, Cu, Cr, Zn, Cd, Pb and Hg etc., and they generally enter water environment by mining, metal smelt, plating, wastewater from chemical industry and sanitary sewage.In China, the Heavy Metal Pollution in Water Environment problem is very general.Surface water heavy metal pollution investigation to the Drinking Water in China water source shows, all kinds of heavy metals such as mercury, and cadmium, the phenomenon that exceeds standard of chromium etc. is serious.Heavy metals exceeding standards such as zinc, lead reach more than 150 times in the bed mud of gulf, Jinzhou, the Bohai Sea.Heavy metal have toxicity big, in environment, be difficult for may producing significant damage to human body by number of ways by metabolism, easily by biological concentration and characteristics such as biological amplification are arranged.Therefore, how effectively to solve heavy metal pollution problem, control heavy metal, become the focus that countries in the world government, enterprise and science researcher pay close attention to the potential health risk that human body causes.
Absorption method is to remove a kind of common method of heavy metal in the water.At present, the sorbing material that is used to remove heavy metal has active carbon, bentonite, zeolite, biological adsorption agent, activated alumina and and natural or synthetic metal oxide and hydrous oxide thereof etc.Wherein metal oxide or its hydrous oxide are because cheap being easy to get, characteristics such as adsorption efficiency height and be subjected to paying close attention to widely, as ferriferous oxide various heavy in the water such as As, Hg, Cd, Pd etc. are had adsorption effect preferably, ferro manganese composite oxides has higher adsorption capacity to As (III) and As (V).Though metal oxide has advantages such as adsorption capacity is big, adsorption rate is fast to heavy metal,, therefore be difficult for utilizing because it generally exists with Powdered.Therefore, how fixing metal oxide makes it become the granular adsorption agent is an important research direction.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of adsorbent of removing heavy metal in the water and preparation method thereof at the problem that above-mentioned prior art exists, the density height of the surface hydroxyl adsorption site of the heavy metal absorbent of the present invention's preparation, high adsorption capacity, the adsorption capacity height, heavy metal contacts with immobilized metal oxide when passing through the duct of macromolecular material, reaches the purpose of removing heavy metal in the water.
For realizing purpose of the present invention, one aspect of the present invention provides a kind of adsorbent of removing heavy metal in the water, comprises following raw material: macromolecular material, metal oxide and pore creating material.
Wherein, the weight portion proportioning of the adsorbent raw material of described heavy metal is macromolecular material 5-25, metal oxide 1-55, pore creating material 0.1-20.
Particularly, the weight portion proportioning of described raw material is: macromolecular material 10-20, metal oxide 2-45, pore creating material 0.1-10.
Wherein, described macromolecular material is selected one or more in polyvinyl fluoride, polyvinyl chloride, polysulfones, polyvinyl alcohol, the cellulose.
Wherein, described metal oxide is selected one or more in iron di-iron trioxide, alundum (Al, zirconium dioxide, manganese dioxide, ceria, FeOOH, hydrated alumina, hydrous zirconium oxide(HZO), the hydroxyl oxidize manganese.
Wherein, described pore creating material is selected one or more in magnesium sulfate, magron, the magnesium perchlorate.
The present invention provides a kind of preparation of adsorbent method of removing heavy metal in the water on the other hand, comprises following step in sequence:
1) prepares raw material according to following weight portion proportioning
Macromolecular material 5-25, metal oxide 1-55, pore creating material 0.1-20
2) macromolecular material is joined in the organic solvent, stir, make Polymer Solution;
3) pore creating material is soluble in water, stir, make pore creating material solution;
4) Polymer Solution and pore creating material solution are mixed back adding metal oxide, make the metal oxide suspension;
5) the metal oxide suspension is splashed in the condensing agent, promptly.
Wherein, the weight portion proportioning of raw material described in the step 1) is: macromolecular material 10-20, metal oxide 2-45, pore creating material 0.1-10; Described macromolecular material is selected one or more in polyvinyl fluoride, polyvinyl chloride, polysulfones, polyvinyl alcohol, the cellulose; Described metal oxide is selected one or more in di-iron trioxide, alundum (Al, zirconium dioxide, manganese dioxide, ceria, FeOOH, hydrated alumina, hydrous zirconium oxide(HZO), the hydroxyl oxidize manganese; Described pore creating material is selected one or more in magnesium sulfate, magron, the magnesium perchlorate.
Wherein, organic solvent step 2) is selected a kind of in acetone, ethanol, the ether; Condensing agent described in the step 5) is selected paraffin, silicone oil or water.
Particularly, macromolecular material step 2) is 1 with the ratio of the weight of organic solvent: 1-10 is preferably 1: 1-6; Pore creating material is 1 with the ratio of the weight of water in the step 3): 1-35 is preferably 1: 5-10; The heavy metal absorbent that makes in the step 5) is a graininess, and its particle diameter is 0.05-5mm.
Further aspect of the present invention provides a kind of heavy metal absorbent that is prepared from according to the method described above.
The de-fluoridation adsorbent composition of the present invention's preparation has following advantage:
1, heavy metal absorbent of the present invention is the compound absorption system that graininess contains metal oxide and macromolecular material, adsorption capacity is big, the removal efficiency of heavy metals height, applied range, be suitable under faintly acid and weak basic condition, carrying out heavy metal absorption, under solutions of weak acidity, when (pH=5), various removal rate of heavy metal are all reached more than 95%.
2, the density height of the surface hydroxyl adsorption site of heavy metal absorbent of the present invention, high adsorption capacity, adsorption capacity height.
3, the stability of heavy metal absorbent of the present invention is high, and metal oxide is completely fixed, and water-fast power is impacted.No matter still be in actual use, all do not have the stripping phenomenon of material, and the cost of macromolecular material and metal oxide be low, the low production cost of adsorbent, suitable wide popularization and application in the regeneration stage.
4, heavy metal absorbent of the present invention adopts different pore creating materials can heighten the molecular material aperture flexibly, and mass transport process control is convenient.
5, the preparation method of the granular heavy metal absorbent of macromolecular material/metal oxide of the present invention is simple, easy and simple to handle, the process conditions gentleness of preparation, product yield height.
The specific embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage of the present invention and characteristics will be more clear along with description.But these embodiment only are exemplary, scope of the present invention are not constituted any restriction.It will be understood by those skilled in the art that and down can make amendment or replace without departing from the spirit and scope of the present invention, but these modifications and replacing all fall within the scope of protection of the present invention the details of technical solution of the present invention and form.
Embodiment 1
1, prepares raw material according to following weight proportion
Macromolecular material 7g, pore creating material 0.5g, metal oxide 10g
Wherein, described macromolecular material is a cellulose acetate; Described pore creating material is a magnesium perchlorate; Described metal oxide is a FeOOH;
2, cellulose acetate adds in the 30g acetone, and is at room temperature even with magnetic stirrer, makes Polymer Solution;
3, magnesium perchlorate is added in the 5g deionized water, at room temperature even with magnetic stirrer, make pore creating material solution;
4, pore creating material solution is joined in the Polymer Solution, at room temperature even with magnetic stirrer, make mixed solution A;
5, FeOOH is joined in the mixed solution A, at room temperature even with magnetic stirrer, make metal-oxide suspension liquid;
6, metal-oxide suspension liquid is splashed in the atoleine of 500ml, because surface tension and gravity effect, drop is frozen into graininess at container bottom, promptly gets heavy metal absorbent.
The water that places 150mL to contain As (III) ion the heavy metal absorbent that makes removes absorption and removes metal ion, wherein, the content of As in the water (III) ion is respectively 1mg/L, adding adsorbent is 2g, under the pH5.5 condition, (temperature was 25 ℃ in 15 minutes in vibration on constant temperature oscillator, oscillation rate is 130r/min), get supernatant, behind 0.45 μ m membrane filtration, with the ICP-OES concentration of remaining heavy metal ion in the clear liquid analytically, can reach more than 98% the clearance of As (III) ion.
Embodiment 2
1, prepares raw material according to following weight proportion
Macromolecular material 10g, pore creating material 1.5g, metal oxide 15g
Wherein, described macromolecular material is a polyvinyl alcohol; Described pore creating material is a magnesium perchlorate; Described metal oxide is FeOOH and ceria, and wherein the ratio of the weight of FeOOH and ceria is 7: 8;
2, polyvinyl alcohol adds in the 40g acetone, and is at room temperature even with magnetic stirrer, makes Polymer Solution;
3, magnesium perchlorate is added in the 10g deionized water, at room temperature even with magnetic stirrer, make pore creating material solution;
4, pore creating material solution is joined in the Polymer Solution, at room temperature even with magnetic stirrer, make mixed solution A;
5, FeOOH and ceria are mixed after, join in the mixed solution A, at room temperature even with magnetic stirrer, make metal-oxide suspension liquid;
6, metal-oxide suspension liquid is splashed in the atoleine of 500ml, because surface tension and gravity effect, drop is frozen into graininess at container bottom, promptly gets heavy metal absorbent.
The water that places 150mL to contain As (V) ion the heavy metal absorbent that makes removes absorption and removes metal ion, wherein, the content of As in the water (V) ion is respectively 0.05mg/L, adding adsorbent is 2g, under pH 5.5 conditions, (temperature was 25 ℃ in 15 minutes in vibration on constant temperature oscillator, oscillation rate is 130r/min), get supernatant, behind 0.45 μ m membrane filtration, with the ICP-OES concentration of remaining heavy metal ion in the clear liquid analytically, can reach more than 99% the clearance of As (V) ion.
Embodiment 3
1, prepares raw material according to following weight proportion
Macromolecular material 8g, pore creating material 1.0g, metal oxide 5g
Wherein, described macromolecular material is a polyvinyl fluoride; Described pore creating material is a magnesium sulfate; Described metal oxide is FeOOH, hydroxyl oxidize manganese, hydrated alumina, hydrous zirconium oxide(HZO), ceria, FeOOH, hydroxyl oxidize manganese, hydrated alumina, hydrous zirconium oxide(HZO), each 1g of ceria;
2, polyvinyl fluoride adds in the 33g acetone, and is at room temperature even with magnetic stirrer, makes Polymer Solution;
3, magnesium sulfate is added in the 10g deionized water, at room temperature even with magnetic stirrer, make pore creating material solution;
4, pore creating material solution is joined in the Polymer Solution, at room temperature even with magnetic stirrer, make mixed solution A;
5, FeOOH, hydroxyl oxidize manganese, hydrated alumina, hydrous zirconium oxide(HZO), ceria are mixed after, join in the mixed solution A, at room temperature even with magnetic stirrer, make metal-oxide suspension liquid;
6, metal-oxide suspension liquid is splashed in the atoleine of 1000ml, because surface tension and gravity effect, drop is frozen into graininess at container bottom, promptly gets heavy metal absorbent.
The water that places 150mL to contain Cu, Cr, Zn, Cd and Pb ion the heavy metal absorbent that makes removes absorption and removes metal ion, wherein, the content of Cu, Cr, Zn, Cd and Pb ion is respectively 0.05mg/L in the water, adding adsorbent is 2g, under pH 5.5 conditions, (temperature was 25 ℃ in 40 minutes in vibration on constant temperature oscillator, oscillation rate is 130r/min), get supernatant, behind 0.45 μ m membrane filtration, with the ICP-OES concentration of remaining heavy metal ion in the clear liquid analytically, can reach more than 95% the clearance of various heavy metal ion.
Claims (10)
1. an adsorbent of removing heavy metal in the water is characterized in that comprising following raw material: macromolecular material, metal oxide and pore creating material.
2. adsorbent as claimed in claim 1 is characterized in that the weight portion proportioning of described raw material is: macromolecular material 5-25, metal oxide 1-55, pore creating material 0.1-20.
3. adsorbent as claimed in claim 1 or 2 is characterized in that the weight portion proportioning of described raw material is: macromolecular material 10-20, metal oxide 2-45, pore creating material 0.1-10.
4. adsorbent as claimed in claim 1 or 2 is characterized in that described macromolecular material selects one or more in polyvinyl fluoride, polyvinyl chloride, polysulfones, polyvinyl alcohol, the cellulose.
5. adsorbent as claimed in claim 1 or 2 is characterized in that described metal oxide selects one or more in di-iron trioxide, alundum (Al, zirconium dioxide, manganese dioxide, ceria, FeOOH, hydrated alumina, hydrous zirconium oxide(HZO), the hydroxyl oxidize manganese.
6. adsorbent as claimed in claim 1 or 2 is characterized in that described pore creating material selects one or more in magnesium sulfate, magron, the magnesium perchlorate.
7. preparation of adsorbent method of removing heavy metal in the water comprises following step in sequence:
1) prepares raw material according to following weight portion proportioning
Macromolecular material 5-25, metal oxide 1-55, pore creating material 0.1-20
2) macromolecular material is joined in the organic solvent, stir, make Polymer Solution;
3) pore creating material is soluble in water, stir, make pore creating material solution;
4) Polymer Solution and pore creating material solution are mixed back adding metal oxide, make the metal oxide suspension;
5) the metal oxide suspension is splashed in the condensing agent, promptly.
8. preparation method as claimed in claim 7 is characterized in that the weight portion proportioning of described raw material is: macromolecular material 10-20, metal oxide 2-45, pore creating material 0.1-10.
9. as claim 7 or 8 described preparation methods, it is characterized in that condensing agent selection paraffin, silicone oil or the water described in the step 5).
10. as claim 7 or 8 described preparation methods, it is characterized in that step 2) described in organic solvent select a kind of in acetone, ethanol, the ether.
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| CN103962088A (en) * | 2014-04-18 | 2014-08-06 | 中国科学院广州地球化学研究所 | SO2-removal efficient adsorbent and preparation method thereof |
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| CN101422720A (en) * | 2008-11-24 | 2009-05-06 | 中国科学院生态环境研究中心 | Absorption filtration dearsenication method based on in-situ composite metal oxides generation |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101422720A (en) * | 2008-11-24 | 2009-05-06 | 中国科学院生态环境研究中心 | Absorption filtration dearsenication method based on in-situ composite metal oxides generation |
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| CN103240064A (en) * | 2013-05-29 | 2013-08-14 | 西南科技大学 | Zirconium/carboxymethylcellulose composite material and preparation thereof |
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