CN101612548B - Method for extracting magnetic minerals to remedy heavy metal pollution of water body with fly ash - Google Patents
Method for extracting magnetic minerals to remedy heavy metal pollution of water body with fly ash Download PDFInfo
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- CN101612548B CN101612548B CN2009101006841A CN200910100684A CN101612548B CN 101612548 B CN101612548 B CN 101612548B CN 2009101006841 A CN2009101006841 A CN 2009101006841A CN 200910100684 A CN200910100684 A CN 200910100684A CN 101612548 B CN101612548 B CN 101612548B
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Abstract
The invention discloses a method for extracting magnetic minerals to remedy heavy metal pollution of water body with fly ash. The fly ash is formulated into mortar to repeatedly extract magnetic minerals in the fly ash by extraction equipment for lots of times; and extracted magnetic minerals are utilized to repeatedly remove the heavy metals in waste water and recover magnetic minerals by the extraction equipment. In the method of the invention, magnetic minerals extraction and removal of heavy metals in water are completed in one system, so the operation is easy, the extraction efficiency is high, and no chemical reagent is needed. The method of the invention organically bonds solid waste treatment with environment remediation of heavy metal pollution, thereby reducing the treatment cost, being capable of repeatedly using adsorbent, and producing no secondary pollution.
Description
Technical field
The invention belongs to useless admittedly the processing and the environmental pollution treatment technology field, be specifically related to a kind of flyash that utilizes and extract the method that magnetic mineral is administered heavy metal pollution in the water body.
Background technology
Water body that industrialization and mankind's activity cause and heavy metal pollution of soil are the serious environmental problems that current mankind faces.Because heavy metal pollution has polyphyly, hysteresis quality, cumulative bad, characteristics such as biodegradable not, and can finally jeopardize human life and health through food chain.Therefore, the improvement of heavy metal pollution is the great task in environmental resource field.At present, according to the principle that heavy metal pollution is administered, heavy metal pollution improvement method mainly contains chemical method, physical-chemical process, bioanalysis and mineral method.Wherein, chemical method (like chemical precipitation method, oxidation-reduction method etc.) is handled heavy metal-polluted dyeing technique and is realized easily, but treatment cost is often higher, be prone to produce secondary pollution; Physical-chemical process (like ion-exchange, electrolysis, absorption method, hyperfiltration etc.) often operate and the cost of raw material higher; Bioanalysis (like microorganism absorption, plant absorbing etc.) is though material is abundant, running cost is low, removal effect good, also is in the laboratory test stage; Mineral method is similar to biological treatment, and surface adsorption, ion-exchange, the duct that utilizes mineral and mineral modified product thereof to have filtered and chemism is administered heavy metal pollution and repairing environment function.Mineral method improvement heavy metal pollution has the mineral wide material sources, cost is low; Can directly can use through machining or through suitable modification and chemical treatment; And the separating process after the absorption is simple; Characteristics such as environment compatibility is good are a kind of resources conservation and environmentally friendly heavy metal pollution processing method.
Heavy metal commonly used is at present administered with environmental mineral has two big types, and the first kind is the metal species mineral, and like natural iron and manganese oxides mineral (iron oxide, troilite, pyrite, pyrolusite etc.), this type mineral are to handling Cr
6+, Cu
2+, Pb
2+, Hg
2+, Cd
2+Deng pollution good effect is arranged.Second type is nonmetallic mineral, if you would take off stone, bentonite, diatomite, zeolite, apatite, clay mineral etc.Wherein iron (hydrogen) oxide mineral extensively exists at nature, particularly bloodstone (α-Fe
2O
3), magnetic iron ore (Fe
3O
4), goethite (alpha-feooh) is because of it has bigger surface area and stronger adsorption capacity, is that Heavy-metal Polluted Environment commonly used is at present administered mineral.Research shows, polar surfaces and the higher specific surface area of utilizing the ferriferous oxide mineral to have, the heavy metal ion of absorption in the environment are a kind of economy, the effective fixing material of water body and heavy metal in soil.
The iron oxide ore thing of in Heavy-metal Polluted Environment is administered, using at present mainly contains two types of artificial synthetic iron oxide and natural iron oxide mineral.Artificial synthetic iron oxide mineral are because of purity is high, fine size, and the removal effect of heavy metal is high, but cost is high, is difficult to large-scale popularization.In recent years; Development is made aggregate with natural minerals or the industrial solid waste residue that is rich in iron oxide; Iron oxide with certain form is fixed on the mineral aggregate surface again, processes through the material of environment mineral material modification, that performance is more excellent as absorption heavy metal and organic pollution.Like clay-magnetic iron ore-Fe (OH)
3The co-precipitation system is as the adsorbent of heavy metal; Utilize chemistry-Re film-coating technique on waste residue, to encapsulate iron oxide, effectively remove As (V) and As (III) etc. as adsorbent.These modifications or synthetic iron oxide material require certain process to handle and operating procedure, and service condition has certain limitation.
At occurring in nature many iron oxide mineral with natural purification function are arranged; Particularly in the industrial solid wastes of many rich iron like flyash, iron tailings, red soil, slag etc.; They are rich in magnetic oxide; Can utilize iron oxide in these solid waste as the fixing new material of heavy metal and organic pollution of absorption, become a kind of new selection.Though directly utilize the fixedly existing successful experience of heavy metal-polluted soil of flyash,, possibly produce secondary pollution etc. because the consumption that processing needs is big.Therefore; The magnetic characteristic that utilizes iron oxide to have can pass through magnetic separation technique, and they are separated from industrial solid wastes effectively; Utilizing the fixing and absorption property of iron oxide to heavy metal, is new thinkings as the environment-friendly materials of administering water body and heavy metal pollution of soil.
Flyash is the abundantest solid waste of China, also is ten minutes serious environmental pollutant, and treating capacity is very big, and the annual emissions of flyash reaches more than 1.6 hundred million tons.Contain a certain amount of in the flyash by magnetic mineral such as bloodstone that forms in the coal burning process and magnetic iron ores; Because industrial solid wastes mineral material reserves are big; The method for distilling of design is simple, with low cost; Operating simple and easy and effective, non-secondary pollution, reach useless admittedly and handle and the environmental improvement combination, is applicable a kind of Heavy-metal Polluted Environment recovery technique on environmental friendliness and the technology.
Summary of the invention
The present invention provides a kind of solid useless utilization and Heavy-metal Polluted Environment reparation to combine low-cost, easy-operating Heavy-metal Polluted Environment restorative procedure.
The concrete steps of the inventive method are:
(1) magnetic mineral extracts:
Flyash and water are mixed with mortar; Extract mortar to high gradient magnetic separator; Magnetic mineral in the mortar is adsorbed in the high gradient magnetic separator; Nonmagnetic portion is discharged the back from high gradient magnetic separator and is continued to extract to the high gradient magnetic separator, extracts through the several times that circulate repeatedly, and the magnetic-particle in the flyash is extracted fully;
(2) magnetic mineral cleans:
Extract clear water to high gradient magnetic separator, the several times repeatedly that circulate utilize other mineral grains that stick on clear water wash cycles pipeline and the magnetic mineral particle; Take off magnetic mineral particle on the high gradient magnetic separator, subsequent use;
(3) heavy metal pollution of water body reparation:
The magnetic mineral that step (2) is obtained with extract to the high gradient magnetic separator after heavy metal polluted waste water mixes, the several times repeatedly that circulate, the magnetic mineral in the discharge of wastewater after the processing, high gradient magnetic separator reclaims.
Described high gradient magnetic separator can adopt existing apparatus; Also can make by oneself; Homemade high gradient magnetic separator simple in structure is made up of 5-6 permanent magnet, and permanent magnet outsourcing plastic foil before using is after magnetic separates completion; Can easily plastic foil be taken off, can prevent that like this magnetic-particle is attached on the permanent magnet.
Described mortar optimum is prepared according to mass ratio 1: 7-12 by flyash and water, and the mortar of this concentration is beneficial to the circulation of mortar and the absorption of magnetic mineral most, excessive concentration, and it is obstructed to circulate, and energy consumption is big, and concentration is low excessively, and extraction efficiency is low.
Described (1) magnetic mineral extracts, (2) magnetic mineral cleans, (3) heavy metal pollution of water body reparation is accomplished in the extraction element that container, peristaltic pump, high gradient magnetic separator and the annulus line of belt stirrer are formed.
Characteristics of the present invention are:
1, the present invention adopts circulation system design, and mortar preparation, magnetic mineral extract, clean and remove in the water heavy metal and all can in a cover system, accomplish, and automaticity is high, easy and simple to handle, do not need chemical reagent.
2, the extraction of the inventive method magnetic mineral is complete, extraction efficiency is high.Flyash after the extraction, magnetic susceptibility is 40 * 10
-8-50 * 10
-8m
3Kg
-1Between, extraction efficiency is more than 90%, and the magnetic mineral purity of extraction is high.
3, solid useless the processing and Heavy-metal Polluted Environment reparation combination, treatment cost is low, and magnetic adsorbent is recyclable, does not produce secondary pollution.
4, the magnetic mineral purposes of extracting is wide, promptly can be used as the adsorbent of heavy metal in the water body, can be used as the fixative of heavy metal in soil again.The magnetic mineral that extracts is air-dry, levigate mistake 100 orders; Apply heavy-metal contaminated soil with 0.1% ratio, control soil moisture time 5-6 month, utilizes the adsorption function of magnetic mineral and redox function that the active heavy metal in the soil is fixed near field capacity.After the heavy-metal contaminated soil reparation finishes, can as required magnetic mineral be reclaimed or stay in the soil.The magnetic mineral reclaimer: soil is air-dry, cross the 2mm sieve, directly utilize the magnetic separator that encapsulates preservative film or freshness protection package that the magnetic mineral in the soil is reclaimed.
Description of drawings
Fig. 1 is the sketch map of the circulatory system of the inventive method.
Fig. 2 is the electron scanning micrograph that extracts the magnetic mineral surface texture in the flyash.
The specific embodiment
As shown in Figure 1, container 1 has agitator 5, and the bottom of container 1 is provided with triple valve 7, and container 1, peristaltic pump 2 and high gradient magnetic separator 3 are communicated with through rubber tube 4, and high gradient magnetic separator 3 is made up of 6 block permanent magnets,
The about 200g of thermal power plant's flyash that collects is placed container 1, add water to about 1: 10 of the ratio of flyash and water; Open agitator 5, stirred 5-10 minute, form uniform flyash mortar with 100-200 rev/min of rotating speed.
Open triple valve 7, set 2 rotating speed 150-200 rev/mins of peristaltic pumps, the flyash mortar gets into annulus line, drives through peristaltic pump 2 and forms flyash mortar circulation; At the uniform velocity through high gradient magnetic separator 3, the magnetic mineral in the mortar is adsorbed on the permanent magnet flyash mortar, opens switch 6, and the nonmagnetic portion in the flyash mortar is got back to container 1 through annulus line; The flyash mortar of getting back to container 1 stirs through agitator 5, drives through peristaltic pump 2 and gets into the circulation loop, carries out the second time and extracts; Separated (disengaging time can be regulated according to the magnetic mineral quantity in the flyash) continuously through 30-60 minute, extract through the circulation repeated multiple times, the magnetic-particle in the flyash is extracted fully, the magnetic mineral extraction rate reached is more than 90% in the flyash.
Permanent magnet outsourcing plastic fresh-keeping membrane or cover freshness protection package, magnetic can take off preservative film or freshness protection package after separating completion easily, can prevent that like this magnetic-particle is attached on the permanent magnet.
Close agitator 5 and peristaltic pump 2, open triple valve 7, will remain the flyash mortar and emit container 1; After the flyash mortar has been put, close triple valve 7; Put into the 1-2L clear water; Open peristaltic pump 2 switches, utilize other mineral grains that stick on clear water wash cycles pipeline and the magnetic mineral particle; Take off magnetic mineral particle on the high gradient magnetic separator, subsequent use.
Take off magnetic mineral particle, put into container 1 through cleaning; Inject heavy metal polluted waste water; Open agitator 5, stirred 5-10 minute; Open triple valve 7, reclaim, the magnetic mineral in the waste water is reclaimed through circulation in 5-10 minute; Waste water after the processing is discharged through triple valve 7.
Embodiment 1
Gather the flyash of 8 the main thermal power plants in Zhejiang Province, use the said extracted method, through 30 minutes circulation extraction magnetic minerals.Flyash magnetic measurement before and after extracting, the magnetic mineral recovery rate is more than 90%, and the magnetized fly-ash rate after the extraction is 42 * 10
-8-56 * 10
-8m
3Kg
-1It mainly is bloodstone and magnetic iron ore that the magnetic mineral that extracts is formed; The magnetic mineral content of 8 thermal power plant's flyash is at 2.2%-16.3%, and the difference of its magnetic mineral content depends primarily on factors such as coal-fired source and ignition temperature.The magnetic mineral that extracts detects through XRD, magnetic survey and SEM, proves that the magnetic mineral type of extracting in the flyash is bloodstone (α-Fe
2O
3) and magnetic iron ore (Fe
3O
4), magnetic susceptibility is 3780 * 10
-8-13082 * 10
-8m
3Kg
-1, SIRM 337.4 * 10
-4-965.9 * 10
-4Am
2Kg
-1
Contain Cd
2+The removal of waste water: use CdSO
4H
2O is made into and contains 50mg/L Cd
2+Solution adds the magnetic mineral 1g/L that extracts in embodiment 1 flyash, removes reaction through 30 minutes and 1 hour, after circulation separates magnetic mineral, through measuring magnetic mineral to Cd
2+Clearance reaches 88% and 89% respectively.
Embodiment 3
Contain Pb
2+The removal of waste water: with Pb (NO
3)
2Be made into and contain 50mg/L Pb
2+Solution adds and use the magnetic mineral 1g/L that this device extracts from halfway up the hill thermal power plant flyash, removes reaction through 30 minutes and 1 hour, after circulation separates magnetic mineral, through measuring Pb
2+Clearance reaches 94 and 98% respectively.
Embodiment 4
Contain Cu
2+And Pb
2+The removal of waste water: use CuSO
4H
2O and Pb (NO
3)
2Be made into and contain 50mg/LCu
2+And Pb
2+Solution adds and use the magnetic mineral 1g/L that this device extracts from halfway up the hill thermal power plant flyash, removes reaction through 30 minutes and 1 hour, after circulation separates magnetic mineral, through measuring Cu
2+Clearance reaches 31% and 32% respectively, Pb
2+Clearance reaches 62% and 66% respectively.
Claims (1)
1. a method of utilizing flyash to extract magnetic minerals to remedy heavy metal pollution of water body comprises the steps:
(1) magnetic mineral extracts:
Flyash and water are mixed with mortar; Extract mortar to high gradient magnetic separator; Magnetic mineral in the mortar is adsorbed in the high gradient magnetic separator, and nonmagnetic portion is discharged the back from high gradient magnetic separator and continued to extract to the high gradient magnetic separator, and several times repeatedly circulate;
(2) magnetic mineral cleans:
Extract clear water to high gradient magnetic separator, the several times repeatedly that circulate utilize other mineral grains that stick on clear water wash cycles pipeline and the magnetic mineral particle; Take off magnetic mineral particle on the high gradient magnetic separator, subsequent use;
(3) heavy metal pollution of water body reparation:
The magnetic mineral that step (2) is obtained with extract to the high gradient magnetic separator after heavy metal polluted waste water mixes, the several times repeatedly that circulate, the magnetic mineral in the discharge of wastewater after the processing, high gradient magnetic separator reclaims;
Described (1) magnetic mineral extracts, (2) magnetic mineral cleans, (3) heavy metal pollution of water body reparation is accomplished in the extraction element that container, peristaltic pump, high gradient magnetic separator and the annulus line of belt stirrer are formed;
Described high gradient magnetic separator is made up of 5-6 permanent magnet, permanent magnet outsourcing plastic foil before using;
The mass ratio of flyash and water is 1 in the described mortar: 7-12.
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|---|---|---|---|
| CN2009101006841A CN101612548B (en) | 2009-07-16 | 2009-07-16 | Method for extracting magnetic minerals to remedy heavy metal pollution of water body with fly ash |
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| CN101612548B true CN101612548B (en) | 2012-04-25 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103240173B (en) * | 2012-02-08 | 2015-11-18 | 香港科技大学 | Magnetic separtor and there is the water treatment system of this magnetic separtor |
| CN103613161B (en) * | 2013-11-27 | 2016-05-18 | 清华大学 | A kind for the treatment of apparatus of the waste water containing arsenic and chromium |
| CN103693710B (en) * | 2014-01-10 | 2015-06-17 | 中国科学院新疆理化技术研究所 | Preparation and oil-water separation method of humic acid modified fly ash magnetic material |
| CN104815621A (en) * | 2015-04-10 | 2015-08-05 | 合肥环照高分子材料厂 | Fly ash-based heavy metal adsorbent and preparation method thereof |
| CN106076257A (en) * | 2016-07-12 | 2016-11-09 | 成都信息工程大学 | One-step method prepares the method for slag municipal sludge magnetic adsorptive material |
| CN109847547A (en) * | 2019-04-08 | 2019-06-07 | 重庆中科检测技术服务有限公司 | A kind of heavy metal chelant and preparation method thereof |
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2009
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Non-Patent Citations (5)
| Title |
|---|
| C. J. Lin et al..PILOT-SCALE STUDIES OF SULFUR AND ASH REMOVAL FROM COALS BY HIGH GRADIENT MAGNETIC SEPARATION.《IEEE Transactions on Magnetics》.1976,第12卷(第5期),第513页实验部分及图2. * |
| C.B.W.Kerkdijk et al..HIGH GRADIENT MAGNETIC SEPARATION OF FLY ASH.《IEEE TRANSACTIONS ON MAGNETICS》.1982,第18卷(第3期),第858页第2节. * |
| E. Maxwell et al..HIGH GRADIENT MAGNETIC SEPARATION OF MINERAL PARTICULATES FROM SOLVENT REFINED COAL.《IEEE Transactions on Magnetics》.1976,第MAG-12卷(第5期),第508页右栏第1段至第3段及图3. * |
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