CN102641725B - Preparation method for material for adsorbing heavy metal - Google Patents
Preparation method for material for adsorbing heavy metal Download PDFInfo
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Abstract
The invention relates to a preparation method for a material for adsorbing heavy metal. Nanoiron, magnesium salt, aluminium salt and caustic soda are adopted as inorganic reactants, sodium diethyldithiocarbamate is adopted as functionalizing agent, the sodium diethyldithiocarbamate and the nanoiron are uniformly mixed, then added into the mixed solution of the caustic soda and the aluminium salt and uniformly mixed, the magnesium salt solution is then slowly added into the solution, mixed for 10 to 30 minutes and kept still for more than 12 hours, blue grey precipitate is separated out, and polyacrylamide is added into the precipitate liquid, so that the material for adsorbing heavy metal is obtained. When 1 to 10 percent by volume of material liquid is added into heavy metal wastewater, the material liquid has excellent adsorptive property and magnetic separation property on heavy metal. The preparation method provided by the invention has the advantages of easy material obtainment, simple process, low cost, good magnetic separation effect and the like, the heavy metal-adsorbing capability of the product is high, and the material can be used in the adsorption treatment of heavy metal wastewater.
Description
Technical field
The present invention relates to a kind of preparation method of the material for Adsorption of Heavy Metals, specifically process the production technology of the sorbing material of heavy metal wastewater thereby.Belong to environmental pollution control field.
Background technology
Heavy metal is generally extensively present in occurring in nature with natural concentration, but along with the mankind are increasing to the exploitation of heavy metal, smelting, processing and business manufacturing activities, cause heavy metal as lead, mercury, cadmium, cobalt etc. enter in atmosphere, water, soil, cause serious environmental pollution.Once heavy metal contaminants enters water body or soil, be just difficult to remove, if enter human body, can produce teratogenesis, carcinogenic harm to human body.Heavy metal pollution is one of maximum water pollution problems of harm, heavy metal wastewater thereby source is mainly that hole, mine internal drainage, waste-rock yard drench immersion, mill tailings draining, non-ferrous metals smelting works' dedusting draining, Non-ferrous Metals Processing Factory's acid washing water, Electroplate Factory's plating piece washings, steel plant's pickling draining, and the industrial processes such as electrolysis, agricultural chemicals, medicine, paint, pigment.The kind of heavy metal in waste water, content and exist form to change greatly with different manufacturing enterprises.It is large that heavy metal has toxicity, is difficult for by metabolism in environment, is easily bioaccumulation and has the features such as biological amplification, not only contaminant water environment, also the serious threat mankind and hydrobiological existence.The minamata disease event of one of famous eight social pollution nuisance, Japan, is exactly because after mercury pollution river, cause biology and crowd along the river to occur mercury poisoning in the world.
China's heavy metal pollution of water body problem is very outstanding, and the pollution rate of river,lake and reservior substrate is up to 80.1%.The Yellow River in 2003, Huaihe River, Song Hua River, the pollution level of the basin sheet heavy metals exceeding standard section of ten large watersheds such as the Liaohe River is super V class.Total copper in bottom mud in Taihu Lakes in 2004, always plumbous, total cadmium content is all in slight pollution level.In the main stream of Huangpu River surface deposit, the super background value of Cd is 2 times, and Pb surpasses 1 times, and Hg content obviously increases; In Suzhou River, Pb all exceeds standard, and Cd 75% exceeds standard, and Hg 62.5% exceeds standard.Urban river has 35.11% section to occur that total mercury surpasses surface water III class water body standard, and 18.46% the total cadmium of stream cross section surpasses III class water body standard, and 25% section has the sample that exceeds standard of total lead to occur.2008, in succession there are 5 arsenic contamination accidents such as Dushan, guizhou county, Chenxi County, Hunan, Guangxi Hechi, Yunnan Yang Zonghai, large Shahe, Henan in China, since in August, 2009, occurred again that Fengxiang, Shaanxi children blood lead exceeds standard, liuyang hunan cadmium pollution and the arsenic contamination accident of Linyi, Shandong.By the Changjiang river, the Zhujiang River, the rivers such as the Yellow River carry into extra large heavy metal contaminants total amount and are about 3.4 ten thousand tons, huge to the contamination hazard of ocean water body.At present, the treatment technology of heavy metal wastewater thereby is mainly contained to two class methods, one class is to make the heavy metal that is dissolved state in waste water be transformed into insoluble precipitated metal thing, through precipitation, from waste water, removes, and comprises neutralization precipitation method, sulphide precipitation, electrodeposit method etc.; The 2nd, the heavy metal in waste water is concentrated with separated under the condition that does not change its chemical form to such as hyperfiltration, electroosmose process, ion-exchange, absorption method etc.These methods can be used alone or in combination according to situations such as waste water quality, the water yields.Design prepares that adsorption efficiency is high, absorption and the good new material of separating property are eliminated heavy metal pollution and had important practical significance.
Summary of the invention
The object of the invention is to disclose a kind of material preparation method for heavy metal adsorption.The material of the Adsorption of Heavy Metals obtaining by the inventive method, for the adsorption treatment of heavy metal wastewater thereby, adsorption capacity is large, easily separated and waste residue is recycling.
To achieve these goals, it is inorganic raw material that the present invention selects magnesium salts, aluminium salt, Nanoscale Iron, caustic soda, and wherein magnesium salts raw material comprises magnesium chloride and magnesium nitrate, and aluminium salt raw material comprises aluminum sulfate and aluminum nitrate.After sodium diethyldithiocarbamate is mixed with Nanoscale Iron, add the mixed solution of aluminium salt and soda ash, after mixing, then with magnesium salt solution hybrid reaction, sediment is the material for Adsorption of Heavy Metals.
Concrete technology is as follows:
The first step, the selection of raw material and preparation
Commercially available technical grade magnesium chloride or magnesium nitrate are added to water, be mixed with weight percent concentration and be 10～30% solution A;
Commercially available technical grade aluminum nitrate or aluminum sulfate are added to water, and to be mixed with weight percent concentration be 5～30% solution B;
By adding water in commercially available technical grade sodium diethyldithiocarbamate, to be mixed with concentration expressed in percentage by weight be 1～2% solution C;
Selecting commercially available Nanoscale Iron is raw material, and in Nanoscale Iron, adding water, to be mixed with concentration expressed in percentage by weight be 1～5% solution D;
Commercially available technical grade caustic soda is added to water, and to make concentration expressed in percentage by weight be 5～20% solution E.
Selecting commercially available technical grade polyacrylamide is flocculation aid.
Above-mentioned Nanoscale Iron is the iron powder of commercially available particle diameter 20nm;
Second step, the preparation of material
First, equivalent measures above-mentioned A, B, C, D, E solution by weight, solution C is mixed with liquid D and within 10～30 minutes, obtain a kind of solution, again solution B is mixed with solution E, stirring and dissolving obtains another kind of solution, then under two kinds of solution being mixed, are stirred, again solution A is slowly added wherein, stirring reaction obtains reactant liquor for 10～30 minutes, by still aging 12～24 hours of reactant liquor, last, at reactor bottom, place magnet piece, after 2 hours, discard clarified solution, the pewter sediment that the bottom of reactor stays, is the material of Adsorption of Heavy Metals;
The 3rd step, the preservation of material or use
The material of this Adsorption of Heavy Metals is added to water, be mixed with the fluent material that percentage by weight is 5～10% Adsorption of Heavy Metals, add polyacrylamide, 0.1～0.5% of the weight of bulk liquid material that the addition of polyacrylamide is Adsorption of Heavy Metals, can be directly used in Adsorption of Heavy Metals again.
Above-mentionedly at reactor bottom, placing magnet piece, is to use 20 centimetres of commercially available diameters, the disk magnet of thick 2 centimetres according to 3000ml reactant liquor, and magnet piece is provided by Shanghai Jin Kun magnetoelectricity Science and Technology Ltd.;
Above-mentioned the 3rd step is directly used in Adsorption of Heavy Metals and is: to heavy metal concentration, be in 1～1000mg/l heavy metal wastewater thereby, to add be weight percentage 5～10% fluent material of the concentration preparing, fluent material dosage is 1～10% percent by volume of wastewater volume, stir 5～30 minutes, in waste water bottom, place 10～20 centimetres of diameters, thickness and be the magnet 10～30 minutes of 1～2 centimetre, adsorption precipitation thing the has been enrichment residue of heavy metal, residue, through high-temperature roasting, obtains available magnetic inorganic material; Heavy metal removing rate 70-100% in heavy metal wastewater thereby.
Advantage of the present invention is as follows:
1. to have technique simple in the present invention, the advantages such as raw material is easy to get, low price.
2. the product counterweight metal that the present invention obtains has good absorption property, comprises Cd, Pb, Hg, Cr, Ni, As, Cu, Zn, Co, Mn etc., and adsorption rate is more than 90%, minimum also over 70%.
3. compare with traditional adsorbent, the material that the present invention obtains can directly be distributed to Adsorption of Heavy Metals in waste water, then separated by magnet, does not need to use the means such as filter, centrifugal, have that effective, speed is fast, the advantages such as power saving that save time, in wastewater treatment, have larger application potential.
4. the present invention removes by heavy metal in heavy metal wastewater thereby the residue of heavy metal that simultaneously obtained enrichment by absorption, and residue becomes available magnetic inorganic material through high-temperature roasting, therefore has society and economic two kinds of benefits.
The specific embodiment
Embodiment 1
The first step, the selection of raw material and preparation
Select commercially available technical grade magnesium chloride or magnesium nitrate, water is added wherein, be mixed with weight percent concentration and be 10% solution, referred to as solution A;
Select commercially available technical grade aluminum nitrate or aluminum sulfate, water is added wherein, be mixed with weight percent concentration and be 20% solution, referred to as solution B;
Select commercially available technical grade sodium diethyldithiocarbamate, water is added wherein, be mixed with concentration expressed in percentage by weight and be 1% solution, referred to as solution C;
Selecting commercially available Nanoscale Iron is raw material, and Nanoscale Iron is the iron powder of particle diameter 20nm, adds water in Nanoscale Iron, and being mixed with concentration expressed in percentage by weight is 1% solution, referred to as solution D;
Commercially available technical grade caustic soda is added to water, and making concentration expressed in percentage by weight is 5% solution, referred to as solution E.
Selecting commercially available technical grade polyacrylamide (molecular weight is 3000000) is flocculation aid.
Second step, the preparation of material
First, equivalent measures above-mentioned A, B, C, D, each 500ml of E solution by weight, and solution C is mixed with solution D 20 minutes, solution B is mixed with solution E, stirring and dissolving, then mixes two liquid, stir again, again solution A is slowly added wherein, stirring reaction 20 minutes, by still aging 12 hours of reactant liquor, last, at reactor bottom, place magnet piece, after 2 hours, discard clarified solution, the pewter sediment that the bottom of reactor stays, is the material of Adsorption of Heavy Metals;
In pewter sediment, add water, be mixed with percentage by weight and be 5% fluent material, then add polyacrylamide, the addition of polyacrylamide is weight of bulk liquid material 0.5%, mixes, and can be directly used in Adsorption of Heavy Metals.
Embodiment 2
Certain laboratory heavy metal containing wastewater treatment: get 1000ml waste water (pH 4.5) in beaker, adding the outward appearance that embodiment 1 prepares is the fluent material 100ml that pewter, content are 5%, stir after 5 minutes, below beaker, pasting end placement diameter is 20cm magnet piece, standing 20 minutes.Testing result shows: in raw wastewater, content of beary metal is respectively 20mg/L Zn, 26mg/L Cu, 6.8mg/L Cd, 3.8mg/L Co, 2.1mg/LCr, 3.8mg/L Ni, processing heavy metal in supernatant is 0.02mg/L Zn, 0mg/L Cu, 0.41mg/L Cd, 0.02mg/L Co, 0mg/L Cr, 0.06mg/L Ni, heavy metal removing rate 94～100%.Therefore, this material has good treatment effect to heavy metal wastewater thereby.
Embodiment 3
Yunnan copper industry heavy metal containing wastewater treatment: get 1000ml waste water (pH 1.53) in beaker, adding the outward appearance that embodiment 1 prepares is the fluent material 200ml that pewter, content are 5%, stir after 5 minutes, below beaker, pasting end placement diameter is 20cm magnet piece, standing 20 minutes.Testing result shows: in raw wastewater, content of beary metal is respectively 15.7mg/L As, 0.55mg/L Cd, 40.3mg/L Cu, 20.9mg/L Zn, in supernatant after processing, heavy metal is 0mg/L As, 0.17mg/L Cd, 0mg/L Cu, 1.13mg/L Zn, heavy metal removing rate 70～100%.
Claims (2)
1. for a preparation method for the material of Adsorption of Heavy Metals, it is characterized in that:
The first step, raw material is selected and preparation
By magnesium chloride, or magnesium nitrate adds water, is mixed with concentration expressed in percentage by weight and is 10～30% solution A; In aluminum nitrate or aluminum sulfate, adding water, to be mixed with concentration expressed in percentage by weight be 5～30% solution B; In sodium diethyldithiocarbamate, adding water, to be mixed with concentration expressed in percentage by weight be 1～2% solution C; In Nanoscale Iron, adding water, to be mixed with concentration expressed in percentage by weight be 1～5% solution D; In caustic soda, adding water, to make concentration expressed in percentage by weight be 5～20% solution E; Selecting commercially available technical grade polyacrylamide is flocculation aid;
Above-mentioned Nanoscale Iron is the iron powder that commercially available particle diameter is 20nm;
Second step, the preparation of material
First, equivalent measures above-mentioned A by weight, B, C, D, E solution, then solution C is mixed with solution D and within 10～30 minutes, obtain a kind of liquid respectively, solution B is mixed with solution E, stirring and dissolving obtains another kind of liquid, then above-mentioned two kinds of liquid are mixed, stir, again solution A is slowly added wherein, stirring reaction obtains reactant liquor for 10～30 minutes, reactant liquor is still aging more than 12 hours, finally, at reactor bottom, place magnet piece, after 2 hours, discard clarified solution, the pewter sediment that the bottom of reactor stays, be the material of Adsorption of Heavy Metals,
Above-mentioned heavy metal is Cd, Pb, Hg, Cr, Ni, As, Cu, Zn, Co, Mn;
The 3rd step, the preservation of material
In the material of this Adsorption of Heavy Metals, add water, be mixed with the liquid that percentage by weight is 5～10% Adsorption of Heavy Metals, add polyacrylamide, 0.1～0.5% of the liquid weight that the addition of polyacrylamide is Adsorption of Heavy Metals, can be directly used in Adsorption of Heavy Metals again.
2. the preparation method of a kind of material for Adsorption of Heavy Metals according to claim 1, is characterized in that: describedly at reactor bottom, placing magnet piece, is to use 20 centimetres of commercially available diameters, the disk magnet metering of thick 2 centimetres according to 3000ml reactant liquor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103801270B (en) * | 2012-11-14 | 2016-03-30 | 长沙飞达矿冶技术有限公司 | For the treatment of the environment-friendly materials and the production technology thereof that contain complicated heavy metal wastewater thereby |
| CN106915812A (en) * | 2015-12-28 | 2017-07-04 | 沈阳中科环境工程科技开发有限公司 | A kind of chemical nickle-plating wastewater inorganic agent and preparation method thereof |
| CN109772277A (en) * | 2019-03-19 | 2019-05-21 | 济南大学 | Adsorbents for lead ion pyrolytic and preparation method thereof in a kind for the treatment of of acidic wastewater |
| CN109847727A (en) * | 2019-03-20 | 2019-06-07 | 武汉山友爆破科技工程有限公司 | A kind of magnetic composite adsorbent and preparation method thereof |
| CN112808239A (en) * | 2021-01-15 | 2021-05-18 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Method for treating heavy metal ions in water body |
| CN112844297A (en) * | 2021-01-15 | 2021-05-28 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Preparation method of magnetic heavy metal ion chelating agent and obtained product |
| CN113072152B (en) * | 2021-06-04 | 2021-09-14 | 赛恩斯环保股份有限公司 | Preparation method and application of defluorination and heavy metal removal polynuclear medicament |
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| EP1044065B1 (en) * | 1997-12-31 | 2002-02-13 | Metal Adsorbens Promotion Company N.V. - in het kort "METAPRO" | Composition of adsorbent |
| CN101327976A (en) * | 2008-07-15 | 2008-12-24 | 南通立源水处理技术有限公司 | Efficient water treatment flocculant |
| CN101962208A (en) * | 2010-10-28 | 2011-02-02 | 上海工程技术大学 | Magnesium-aluminum-iron hydrotalcite, preparation method and application thereof as coadsorbent |
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| HUP0200307A2 (en) * | 2002-01-29 | 2004-01-28 | Rezes Zoltán | Absorbent for purification of water, drinking-water |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1044065B1 (en) * | 1997-12-31 | 2002-02-13 | Metal Adsorbens Promotion Company N.V. - in het kort "METAPRO" | Composition of adsorbent |
| CN101327976A (en) * | 2008-07-15 | 2008-12-24 | 南通立源水处理技术有限公司 | Efficient water treatment flocculant |
| CN101962208A (en) * | 2010-10-28 | 2011-02-02 | 上海工程技术大学 | Magnesium-aluminum-iron hydrotalcite, preparation method and application thereof as coadsorbent |
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