CN105110445B - A kind of method for handling heavy metal wastewater thereby - Google Patents
A kind of method for handling heavy metal wastewater thereby Download PDFInfo
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- CN105110445B CN105110445B CN201510582084.9A CN201510582084A CN105110445B CN 105110445 B CN105110445 B CN 105110445B CN 201510582084 A CN201510582084 A CN 201510582084A CN 105110445 B CN105110445 B CN 105110445B
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Abstract
The invention discloses a kind of method for handling heavy metal wastewater thereby, it is characterized in that：Clayey dolomite ore reduction sieving, 0.5~2mm particulate matter is obtained, particulate matter and/or its high-temperature calcination product are loaded into filter tank or filter post, heavy metal-containing waste water is handled with filter type.The present invention is made up of and with natural nano-porous structure characteristic using clayey dolomite nano-mineral attapulgite dolomite, the reaction of water mineral interface occurs inside particle, nano-dolomite induction heavy metal therein hydrolyzes to form hydroxide or subcarbonate precipitation, nano bar-shape attapulgite plays hydrolyzed colloidal particle adsorption-condensation effect, and pH value of waste water, content of beary metal after processing stably reach discharge standard；Heavy metal waste after processing can be used for metal recovery, or be changed into stable silicate in 500~700 DEG C of thermal technology's processing.
Description
Technical field
Technical field is utilized the invention belongs to wastewater treatment and nonmetal mineral resource, is related to material for water treatment and method.
Background technology
There is the waste water containing heavy metal of hundreds of billion cubic meters in China every year, including mine, smelting, electrolysis, plating, agricultural chemicals,
The waste water of the industry such as medicine, paint, chemical industry, pigment.River and lake stream deposit caused by heavy metal wastewater thereby discharge, especially
Soil has been not only broken up ecological environment by heavy metal pollution, and can enter human body by food chain enrichment, has become
Threaten the formidable enemy of human body health.
The processing method of heavy metal wastewater thereby can be divided into two major classes both at home and abroad at present：One class is to make to be in dissolved state in waste water
Heavy metal ion be changed into insoluble heavy metal compound, then removed by precipitation or FLOTATION SEPARATION from waste water.Conventional
Method has hydroxide precipitation method, sulphide precipitation, ferrite coprecipitation, redox precipitation method, ion floatation method, electricity
Solution, diaphragm process, bioanalysis etc..The most frequently used in these methods is hydroxide precipitation method, sulphide precipitation, ferrite
Coprecipitation and redox precipitation method.But the problem of existing jointly is that precipitation particle is tiny, it is necessary to which sedimentation basin, newborn tiny
Grain is difficult to be completely separated from the water, and water treatment efficiency is unstable, and precipitating sludge belongs to dangerous waste, and sludge quantity is big, and moisture content is high,
Treatment of Sludge is difficult.In sulphide precipitation, precipitating reagent is difficult that control is appropriate, easily causes secondary pollution.Ion floatation method, electricity
The several methods such as solution, diaphragm process because processing cost height, system complex, it is difficult in maintenance be rarely employed.
Another kind of method is to be adsorbed, concentrated and separated under conditions of heavy metal ion chemical form is not changed, tool
Body method has hyperfiltration, electroosmose process, membrane separation process, evaporation concentration method, absorption method, ion-exchange, solvent extraction etc.,
Wherein extensive concern is absorption method.The material that Heavymetal Wastewater Treatment by Adsorption is generally used is cheap mineral material, such as swollen
Moisten soil, zeolite, sepiolite, attapulgite, magnetic iron ore, goethite etc..These mineral materials or modified product are in waste water
Cd2+、Pb2+、Hg2+、Cu2+Deng with stronger suction-operated, but adsorption capacity is limited, and content of beary metal is only in solid after processing
For 1-5%, the requirement of recycling is not reached, heavy metal is unstable in waste, easy dissolution causes secondary pollution, turns on the contrary
Dangerous waste, the cost that the solid waste containing heavy metal is disposed again is very high, also relatively difficult.
The content of the invention
The present invention be for avoid the weak point present in above-mentioned prior art there is provided it is a kind of processing containing heavy metal ion
The material and method of waste water, to time of the stable processing, advanced treating, harmless treatment and the resource that reach heavy metal wastewater thereby
Receive.
The technical proposal for solving the technical problem of the invention is：
The method of present invention processing heavy metal wastewater thereby, is characterized in：
The clayey dolomite of output in Attapulgite clay layer is selected as raw material, in the clayey dolomite
Dolomite content is 55~65%, and the content of attapulgite and opal is 35~45%；
Clayey dolomite is crushed, screening obtains clayey dolomite particulate matter of the particle diameter in 0.5~2mm；
Filter tank is loaded using the clayey dolomite particulate matter as filler；Or, the clayey dolomite particle
Thing calcines 30~120min at 500~900 DEG C, calcined clay matter dolomite particulate matter is obtained, with the calcined clay matter white clouds
Rock particulate matter loads filter tank as filler；Or, clayey dolomite particulate matter is pressed with calcined clay matter dolomite particulate matter
According to mass ratio 1:1~5:After 1 ratio mixing filter tank is loaded as filler；
Heavy metal wastewater thereby, clayey dolomite particle therein are handled with 0.5~3h of hydraulic detention time filter type
Thing and/or the slow aquation release hydroxyl of calcined clay matter dolomite particulate matter, improve the pH value of water between 8~9, promote a huge sum of money
Category ion hydrolyzes to form hydroxide precipitation or subcarbonate precipitation；
When concentration of heavy metal ion exceedes national heavy metals discharge standard in water outlet, 1~5cm is added in filter tank
Thick clayey dolomite particulate matter and/or calcined clay matter dolomite particulate matter, proceeds wastewater treatment；
When filter tank filler can not with water heavy metal ion occur precipitation reaction when, or because hydroxide precipitation or
When subcarbonate precipitation is largely gathered and blocked：Liquid in filter tank is discharged, it is 5 that mass concentration is added into the filter tank
~10% hydrochloric acid or sulfuric acid, to dissolve the hydroxide and subcarbonate in filter tank, forms lysate, what electrolysis was obtained
Lysate is to reclaim heavy metal；Or take out including the filler that fails, hydroxide and the solid matter of subcarbonate in filter tank,
Solid matter is handled in 500~700 DEG C of thermal technologies, hydroxide and subcarbonate is changed into stable silicate, is eliminated
The secondary pollution of heavy metal.
Heavy metal ion includes Cd in the heavy metal wastewater thereby2+、Pb2+、Cu2+、Co2+、Ni2+、Zn2+、Mn2+And/or Fe2+,
Concentration of heavy metal ion is 0.5~200mg/L in the heavy metal wastewater thereby.
The positive effect of the present invention is embodied in：
Clayey dolomite in high resolution scanning electron microscopy study discovery Attapulgite clay is by nano-mineral concave convex rod
Stone-dolomite composition (Fig. 1), with natural nano-porous structure characteristic (Fig. 2).Heavy metal in waste water can be diffused into
Water-mineral interface reaction occurs inside particle, reaction specific surface area is improved.
Essential mineral component is nano-dolomite in clayey dolomite, high, quick neutralization waste water with reactivity
Acidic materials and the effect for improving pH value of waste water, promote heavy metal ion hydrolytic precipitation and exchange the hydrogen-oxygen that precipitation forms heavy metal
Compound or subcarbonate.Due to dissolving the cushioning effect of carbonate, aqueous solution pH is maintained between 6-7, not only water outlet
PH stable, and be conducive to precipitating crystalline be grown to serve as coarse grain crystal, mitigate because fine colloidal solid precipitation is to hole
Blocking and the cladding to material surface.
Strength test shows that the material granule has certain intensity and water resistance, can be as active filter with the side of filtering
Formula handles heavy metal-containing waste water, and not only materials'use is convenient, and avoids sludge dewatering process complicated after processing waste water.
When the heavy metal in waste water is Cu2+、Co2+、Ni2+During Deng being worth higher metal, consolidating after processing heavy metal wastewater thereby
Body is directly dissolved in filter post with diluted acid, and the valuable heavy metal of lysate electrolytic recovery, solid residue is abandoned as waste.
The highly active protein stone of nano bar-shape attapulgite, impalpable structure in clayey dolomite is in processing heavy metal
Do not reacted substantially during waste water, residual is in solids.But attapulgite, albumen after processing waste water in solid
Combination reaction formation chemical property stabilization can occur under relatively low calcining heat with heavy metal hydroxide, carbonate for stone
Silicate.When the heavy metal in waste water is Cd2+、Pb2+、Zn2+、Mn2+、Fe2+Deng low value metal when, remove failure solids
Matter, the 500-700 DEG C of calcining in high temperature furnace, heavy metal therein and attapulgite, the silicic acid of opal chemical combination formation heavy metal
Salt thing phase, prevents and treats heavy metal secondary pollution.
Brief description of the drawings
Fig. 1 is that (P represents attapulgite characteristic diffraction peak to the dolomitic X ray diffracting spectrum of clayey in figure, and D represents white
Marble characteristic diffraction peak)；
Fig. 2 is the dolomitic field emission scanning electron microscope image of clayey, and showing nano-dolomite, (rhombohedral is brilliant
Body), attapulgite (bar-shaped, pencil crystal) mix inside intergrowth, DOLOMITE CRYSTALS and cavity generally occur, with natural nanometer
Loose structure characteristic.
Embodiment
The non-limiting implementation steps of the present invention are as follows：
Embodiment 1
The present embodiment, which is prepared, contains Pb2+、Zn2+、Mn2+、Fe2+Each 5mg/L heavy metal wastewater thereby, adjustment waste water pH value be
4.5-5, as simulation heavy metal wastewater thereby, is handled as follows：
The clayey dolomite that a, selection are made up of nano-mineral attapulgite-dolomite, dolomite content 60% is concavo-convex
The content 40% of rod stone and opal；
B, the clayey dolomite particulate matter that clayey dolomite is broken, screening obtains 0.5~1mm；
C, clayey dolomite particulate matter is loaded into diameter 20mm, effective depth 500mm filter post；
D, the filtering velocity filtration treatment simulation heavy metal wastewater thereby with hydraulic detention time 1h, weekly 2 detection water outlets of water sampling
Pb2+、Zn2+、Mn2+、Fe2+Concentration, lasts 110 days testing results and shows Pb2+<0.5mg/L、Zn2+<0.5mg/L、Mn2+<0.1mg/
L、Fe2+<0.1mg/L, water outlet pH value and concentration of heavy metal ion meet discharge standard.
After e, experiment post are run 130 days, Zn in water outlet2+Concentration exists solid in filter post more than 2.0mg/L, material failure
600 DEG C of thermal technology's processing, heavy metal is changed into stable silicate, eliminates the secondary pollution of heavy metal.
Embodiment 2
The present embodiment, which is prepared, contains Cu2+50mg/L heavy metal wastewater thereby, the pH value of adjustment waste water is 4.5-5, is used as simulation weight
Metallic wastewater, is handled as follows：
The clayey dolomite that a, selection are made up of nano-mineral attapulgite-dolomite, dolomite content 65% is concavo-convex
The content 35% of rod stone and opal；
B, the clayey dolomite particulate matter that clayey dolomite is broken, screening obtains 0.5~1mm；Take part of clay
Matter dolomite calcines 120min at 900 DEG C, obtains calcined clay matter dolomite particulate matter；
C, clayey dolomite particulate matter and calcined clay matter dolomite particulate matter according to mass ratio 2:1 is loaded into diameter
In 20mm, effective depth 500mm filter post；
D, the filtering velocity filtration treatment simulation heavy metal wastewater thereby with hydraulic detention time 10min, atomic absorption spectrophotometry
Detect water outlet Cu2+, pH, last 94 days testing results and show water outlet pH value between 8-9, Cu2+<0.5mg/L, concentration meets row
Put standard.
After e, experiment post are run 120 days, Cu in water outlet2+Concentration is out of service more than 1mg/L, liquid in discharge filter post, to
The sulfuric acid for adding that mass concentration is 3% in post is filtered, hydroxide therein and carbonate is dissolved, lysate is formed, for being electrolysed
Reclaim copper.
Embodiment 3
The present embodiment takes acid water containing heavy metal as simulation heavy metal wastewater thereby, its cupric from certain Porphyrite iron ore sour water storehouse
47mg/L, pH value 2.8, are handled as follows：
The clayey dolomite that a, selection are made up of nano-mineral attapulgite-dolomite, dolomite content 55% is concavo-convex
The content 45% of rod stone and opal；
B, the clayey dolomite particulate matter that clayey dolomite is broken, screening obtains 0.5~2mm, in 600 DEG C of calcinings
120min, obtains calcined clay matter dolomite particulate matter；
C, calcined clay matter dolomite particulate matter is loaded into diameter 20mm, effective depth 500mm filter post；
D, the filtering velocity filtration treatment simulation heavy metal wastewater thereby with hydraulic detention time 1h, calcined clay matter dolomite therein
The slow aquation release hydroxyl of particulate matter, improves the pH value of water between 8~9, the water outlet copper ion concentration in 46 days<0.5mg/L,
Meet state sewage emission standard.
E, operation 57 days after, copper ion concentration in water outlet>1.0mg/L, is handled solid in filter post in 600 DEG C of thermal technologies, weight
Metal Phase Transition is stable silicate, eliminates the secondary pollution of heavy metal.
Claims (1)
1. a kind of method for handling heavy metal wastewater thereby, it is characterized in that：
The clayey dolomite of output in Attapulgite clay layer is selected as raw material, the white clouds in the clayey dolomite
Stone content is that the content of 55~65%, attapulgite and opal is 35~45%；
The clayey dolomite particulate matter that the clayey dolomite is broken, screening obtains 0.5~2mm；
Filter tank is loaded using the clayey dolomite particulate matter as filler；Or, the clayey dolomite particulate matter is existed
500~900 DEG C of 30~120min of calcining, obtain calcined clay matter dolomite particulate matter, with the calcined clay matter dolomite
Grain thing loads filter tank as filler；Or, clayey dolomite particulate matter and calcined clay matter dolomite particulate matter according to matter
Measure ratio 1~5:After 1 ratio mixing filter tank is loaded as filler；
Heavy metal wastewater thereby is handled with 0.5~3h of hydraulic detention time filter type, clayey dolomite particulate matter therein and/
Or calcined clay matter dolomite particulate matter slow aquation release hydroxyl, improve the pH value of water between 8~9, promote heavy metal from
Son hydrolyzes to form hydroxide precipitation or subcarbonate precipitation；
When concentration of heavy metal ion exceedes discharge standard in water outlet, the thick clayey dolomites of 1~5cm are added in filter tank
Grain thing and/or calcined clay matter dolomite particulate matter, proceed heavy metal containing wastewater treatment；
When no longer with the heavy metal ion in water precipitation reaction occurs for filter tank filler, or because of hydroxide precipitation or alkali formula
When carbonate deposition is largely gathered and blocked：Discharge filter tank in liquid, into the filter tank add mass concentration be 5~
10% hydrochloric acid or sulfuric acid, to dissolve the hydroxide and subcarbonate in filter tank, forms lysate, it is molten that electrolysis is obtained
Liquid is solved to reclaim heavy metal；Or solid matter in filter tank is taken out, solid matter is handled in 500~700 DEG C of thermal technologies, makes hydrogen-oxygen
Compound and subcarbonate are changed into stable silicate, eliminate the secondary pollution of heavy metal；
Heavy metal ion includes Cd in the heavy metal wastewater thereby2+、Pb2+、Cu2+、Co2+、Ni2+、Zn2+、Mn2+And/or Fe2+, it is described
Concentration of heavy metal ion is 0.5~200mg/L in heavy metal wastewater thereby.
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| CN107456944A (en) * | 2017-09-26 | 2017-12-12 | 南京乐透思环保科技有限公司 | A kind of inorganic composite materials, preparation method and its purposes for being used for heavy-metal ion removal in sewage disposal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105565455A (en) * | 2016-02-01 | 2016-05-11 | 浙江大学 | Method for treating heavy metal waste water with inorganic flocculant |
| CN105858832A (en) * | 2016-04-12 | 2016-08-17 | 合肥工业大学 | Heavy metal wastewater treatment material and method thereof |
| CN105776366B (en) * | 2016-04-12 | 2019-01-22 | 合肥工业大学 | A kind of material and method handling lead waste water |
| CN106277168A (en) * | 2016-09-20 | 2017-01-04 | 孙冠州 | A kind of water quality cleansing agent and manufacture method thereof |
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| SK283214B6 (en) * | 1998-07-22 | 2003-03-04 | Ipres In�Iniering, S. R. O. | Sorbent, its production method and use for immobilisation of heavy metal in contaminated liquid and solid phase |
| JP2004049952A (en) * | 2002-07-16 | 2004-02-19 | Ube Material Industries Ltd | Treatment method for acidic wastewater |
| EP2286910A1 (en) * | 2009-08-19 | 2011-02-23 | King Abdulaziz City for Science and Technology | Adsorbent and filter unit |
| JP5187376B2 (en) * | 2010-04-22 | 2013-04-24 | 吉澤石灰工業株式会社 | Removal agent for heavy metal ions in waste water and method for removing heavy metal ions using the same |
| JP5257469B2 (en) * | 2011-02-01 | 2013-08-07 | 吉澤石灰工業株式会社 | Remover of harmful substances in waste water and removal method using the same |
| CN102621258B (en) * | 2012-04-09 | 2016-08-03 | 中国科学院生态环境研究中心 | A kind of heavy metal chromium form fractionation method |
| CN104383873B (en) * | 2014-11-13 | 2016-08-24 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Utilize the method that low-grade attapulgite clay prepares compound adsorbent |
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| CN107456944A (en) * | 2017-09-26 | 2017-12-12 | 南京乐透思环保科技有限公司 | A kind of inorganic composite materials, preparation method and its purposes for being used for heavy-metal ion removal in sewage disposal |
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