CN103991986A - Method for removing thallium in copper effluent - Google Patents
Method for removing thallium in copper effluent Download PDFInfo
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- CN103991986A CN103991986A CN201410241943.3A CN201410241943A CN103991986A CN 103991986 A CN103991986 A CN 103991986A CN 201410241943 A CN201410241943 A CN 201410241943A CN 103991986 A CN103991986 A CN 103991986A
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Abstract
The invention discloses a method for removing thallium in a copper effluent. The technical scheme adopted by the method is as follows: firstly, feeding an oxidant bleaching powder and a coagulant polyferric sulfate/polyaluminum chloride/polyaluminum ferric sulfate (PFS/PAC/PAFS) to a copper effluent; oxidizing univalent thallium in a dissolved state in the copper effluent into trivalent thallium under an aeration or agitation condition and forming a thallium hydroxide sediment, and then feeding a coagulant polyacrylamide (PAM) to a reaction liquid; forming easy-to-precipitate large particles from difficult-to-precipitate small particles by using the bridging and net capturing action of the coagulant; finally carrying out solid-liquid separation by virtue of a solid-liquid separation device. Thus, efficient removal of thallium is achieved.
Description
One. technical field
The present invention relates to water-treatment technology field, especially relate to the processing of cave effluent, specifically a kind of method of removing heavy metal thallium in cave effluent.
Two. background technology
Thallium (Tl) is very low in the abundance of occurring in nature, be only 0.75mg/kg, but its toxicity is much larger than Hg, Cd, Pb and As, is only second to methyl mercury.Tl and compound thereof have been put into the monitoring index system of water body priority pollutants Black List and China's water environment quality standard (GB3838-2002).Some mine will produce containing thallium cave effluent in recovery process, if directly discharge without processing, can affect downstream river basin water quality safety; If for field irrigation, can affect crops quality and HUMAN HEALTH.Therefore be, the important leverage of safeguarding Mine ecology safety to the improvement containing thallium cave effluent.
But, in waste water, the treatment process of thallium is still rare at present, the method of the processing waste water containing thallium that Environmental Protection Agency is recommended is mainly to utilize activated alumina and ion exchange method to carry out fractionation by adsorption, but processing cost is high, is difficult to be widely applied containing in the treating processes of thallium cave effluent a large amount of.State Intellectual Property Office's Granted publication on December 23rd, 1992 a kind of patent of invention of " treatment process of waste water containing thallium " (publication number: CN 1067229A).The technical characteristics of this patent is: waste water containing thallium acid adding is adjusted pH to 2～5, then adds successively oxygenant (clorox/hydrogen peroxide/bromine water/chlorine), coprecipitator and alkali.The disclosed technical scheme water outlet thallium of this patent is less than 50ug/L, if for processing and have the following disadvantages containing thallium cave effluent: be everlasting between 6～8 containing thallium cave effluent pH value (1), therefore, when processing, need first use acid for adjusting pH value, final outflow water regulates pH value with alkali again, causes soda acid waste, complex treatment process, long flow path; (2) its reagent cost of selected oxygenant is higher; (3) water outlet thallium is higher than 0.1ug/L, and water outlet does not meet water environment quality standard requirement.State Intellectual Property Office has announced a kind of patent of invention of " emergency processing method of thallium polluted raw " (publication number: CN 102107969A) on June 29th, 2011.The technical characteristics of this patent is: waste water containing thallium adds potassium permanganate or potassium permanganate+clorox, ozone, PAC successively.The disclosed technical scheme water outlet thallium of this patent is less than 0.1ug/L, but still has the following disadvantages: (1) water outlet manganese and colourity easily exceed standard, and easily form secondary pollution; (2) ozonize cave effluent, ozone devices investment is large, running cost is high.
Therefore, seek a kind of simple to operate, processing cost is low, does not introduce detrimental impurity, be applicable to having important practical significance containing the chemical treatment technology of thallium cave effluent.
Three. summary of the invention
In order to reach above object, the technical solution used in the present invention is first to adding oxidant bleach powder and coagulating agent PFS/PAC/PAFS containing in thallium cave effluent, under aeration or agitation condition, the monovalence thallium of solubilised state in cave effluent is oxidized to trivalent thallium and forms thallic hydroxide throw out, and then add flocculation agent PAM in reaction solution, utilize bridge formation, the net effect of catching of flocculation agent to make the small-particle of difficult precipitation become the macrobead of easy precipitation, finally carry out solid-liquid separation by equipment for separating liquid from solid, realize the efficient removal of thallium.
A kind of method of removing heavy metal thallium in cave effluent of the present invention, specifically comprises the following steps:
(1) oxidation, coagulation process: to adding chlorinated lime and PFS/PAC/PAFS etc. containing in thallium cave effluent, and aeration or stirring reaction for some time.In order to reach most economical treatment effect, reacting liquid pH value is controlled between 7～9, chlorinated lime by 50～100g/m3 add, PFS/PAC/PAFS adds by 3～10g/m3, more than aeration or stirring reaction time is controlled at 30min.
(2) Flocculation Settling Process: add PAM under aeration or agitation condition in above-mentioned reaction solution.In order to reach good treatment effect, PAM adds by 0.1～1.5g/m3, more than the flocculating settling time is controlled at 60min, and the throw out part after flocculating settling is back in above-mentioned reaction solution.
(3) solid-liquid separation process: the supernatant liquor after above-mentioned flocculating settling is filtered, further reduce the content of water outlet thallium by the suspended substance in removal supernatant liquor.Filter plant can be selected sand-bed filter, fiber ball filter, Gore membrane filtration device etc.The backwashing water that underflow after flocculating settling and filtration produce carries out press filtration by plate-and-frame filter press.
The invention has the advantages that:
(1) adopt conventional dose chlorinated lime to make oxygenant, there is low, the easy purchase of cost, can not introduce the features such as new detrimental impurity.
(2) treatment process meets cave effluent water quality characteristics especially, without carrying out acid-alkali medium conversion, has avoided adding of soda acid, has feature simple to operate, processing technological flow is short.
(3) adopt underflow backflow control techniques for cave effluent water quality characteristics, and adopt mechanical filter equipment to carry out degree of depth oil removal to supernatant liquor, realized the efficient thallium that removes, guaranteed that water outlet thallium is less than 0.1ug/L.
Four. brief description of the drawings
Fig. 1 is a kind of process flow sheet of removing the method for heavy metal thallium in cave effluent of the present invention.
Technical process of the present invention shown in figure is mainly: mine is adopted the cave effluent (1) producing in smelting process and risen to water collecting basin (2) by pump, enter into aeration tank (3) by by-pass valve control, in aeration tank (3), add successively chlorinated lime (a) consumption 50～100g/m3 and PFS/PAC/PAFS (b) consumption 3～10g/m3, blast aeration reaction 30～60min, reaction solution (4) enters settling tank (5), carry out flocculating settling to adding flocculation agent PAM (c) consumption 0.1～1.5g/m3 in settling tank (5), throw out (6) part after flocculating settling is back to aeration tank (3), supernatant liquor after sedimentation (7) enters Buffer Pool (8), water in Buffer Pool (8) enters strainer (9) by water pump effect and carries out deep purifying processing, water purification (10) standard discharge.Sediment (11) in aeration tank (3), settling tank (5) and strainer (9) enters the unit that delivers to qualification after press filteration system is processed and centrally disposes.
Five. embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the present invention is described in further detail.
Embodiment 1
Cave effluent in water collecting basin enters aeration tank by by-pass valve control, in aeration tank, add successively chlorinated lime and PFS, dosage is respectively 100g/m3 and 3g/m3, aerated reaction 30min, utilize aeration agitation effect to make medicament and the abundant hybrid reaction of waste water, supernatant liquor overflow enters settling tank, in settling tank, add flocculation agent PAM, dosage is 0.10g/m3, at the bridge formation of flocculation agent, the lower small-particle flco of the net effect of catching becomes the macrobead of easy precipitation, throw out part after flocculating settling is back in the reaction solution of aeration tank, supernatant liquor after sedimentation enters strainer, further reduce the content of water outlet thallium by the suspended substance in removal supernatant liquor.
Result shows: cave effluent thallium content is that 18.15ug/L, arsenic content are 0.17mg/L, after the present embodiment method is processed, thallium content is reduced to 0.05ug/L, arsenic content is reduced to below 0.001mg/L, and after processing, water outlet reaches the water quality requirement that " water environment quality standard " GB3838-2002 of country specifies.
Embodiment 2
Cave effluent in water collecting basin enters aeration tank by by-pass valve control, in aeration tank, add successively chlorinated lime and PFS, dosage is respectively 50g/m3 and 10g/m3, aerated reaction 60min, utilize aeration agitation effect to make medicament and the abundant hybrid reaction of waste water, supernatant liquor overflow enters settling tank, in settling tank, add flocculation agent PAM, dosage is 1.5g/m3, at the bridge formation of flocculation agent, the lower small-particle flco of the net effect of catching becomes the macrobead of easy precipitation, throw out part after flocculating settling is back in the reaction solution of aeration tank, supernatant liquor after sedimentation enters strainer, further reduce the content of water outlet thallium by the suspended substance in removal supernatant liquor.
Result shows: cave effluent thallium content is that 3.34ug/L, arsenic content are 0.11mg/L, after the present embodiment method is processed, thallium content is reduced to 0.04ug/L, arsenic content is reduced to 0.0012mg/L, and after processing, water outlet reaches the water quality requirement that " water environment quality standard " GB3838-2002 of country specifies.
Embodiment 3
Cave effluent in water collecting basin enters aeration tank by by-pass valve control, in aeration tank, add chlorinated lime, dosage is 50g/m3, aerated reaction 60min, utilize aeration agitation effect to make medicament and the abundant hybrid reaction of waste water, supernatant liquor overflow enters settling tank, in settling tank, add flocculation agent PAM, dosage is 0.19g/m3, at the bridge formation of flocculation agent, the lower small-particle flco of the net effect of catching becomes the macrobead of easy precipitation, throw out part after flocculating settling is back in the reaction solution of aeration tank, supernatant liquor after sedimentation enters strainer, further reduce the content of water outlet thallium by the suspended substance in removal supernatant liquor.
Result shows: cave effluent thallium content is that 2.38ug/L, arsenic content are 0.19mg/L, after the present embodiment method is processed, thallium content is reduced to 0.06ug/L, arsenic content is reduced to 0.012mg/L, and after processing, water outlet reaches the water quality requirement that " water environment quality standard " GB3838-2002 of country specifies.
Claims (4)
1. a method of removing heavy metal thallium in cave effluent, is characterized in that: step and processing condition are as follows:
(1) oxidation, coagulation process: to adding chlorinated lime and PFS/PAC/PAFS etc. containing in thallium cave effluent, and aeration or stirring reaction for some time;
(2) Flocculation Settling Process: add PAM under aeration or agitation condition in above-mentioned reaction solution;
(3) solid-liquid separation process: the supernatant liquor after above-mentioned flocculating settling is filtered, further reduce the content of water outlet thallium by the suspended substance in removal supernatant liquor.
2. a kind of method of removing heavy metal thallium in cave effluent according to claim 1, it is characterized in that: in oxidation, coagulation process, reacting liquid pH value is controlled between 7～9, chlorinated lime by 50～100g/m3 add, PFS/PAC/PAFS adds by 3～10g/m3, more than aeration or stirring reaction time is controlled at 30min.
3. a kind of method of removing heavy metal thallium in cave effluent according to claim 1, it is characterized in that: in Flocculation Settling Process, PAM adds by 0.1～1.5g/m3, more than the flocculating settling time is controlled at 60min, and the throw out part after flocculating settling is back in above-mentioned reaction solution.
4. a kind of method of removing heavy metal thallium in cave effluent according to claim 1, is characterized in that: in solid-liquid separation process, filter plant can be selected sand-bed filter or fiber ball filter or Gore membrane filtration device; The backwashing water that underflow after flocculating settling and filtration produce carries out press filtration by plate-and-frame filter press.
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| CN201410241943.3A CN103991986A (en) | 2014-05-30 | 2014-05-30 | Method for removing thallium in copper effluent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192977A (en) * | 2014-08-21 | 2014-12-10 | 华南理工大学 | Method for deeply removing thallium in water body through hydrodynamic cavitation assisted oxidation |
| CN104310672A (en) * | 2014-10-27 | 2015-01-28 | 湖南净源环境工程有限公司 | Thallium-containing wastewater strongly oxidizing, coagulating, adsorbing and recovering process |
| CN104310593A (en) * | 2014-10-17 | 2015-01-28 | 紫金矿业集团股份有限公司 | Biological treatment method for thallium in pit water |
| CN104803509A (en) * | 2015-04-10 | 2015-07-29 | 深圳中清环境科技有限公司 | Treatment process and treatment equipment for heavy metal wastewater containing thallium |
| CN108706785A (en) * | 2018-08-10 | 2018-10-26 | 大冶有色金属有限责任公司 | A kind of mining smelting wastewater exception water quality emergency treatment device and method |
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| CN102311190A (en) * | 2011-08-19 | 2012-01-11 | 深圳市水务(集团)有限公司 | Method for removing thallium from drinking water by enhanced conventional water treatment process |
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2014
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| JP2007117965A (en) * | 2005-10-31 | 2007-05-17 | Sumitomo Osaka Cement Co Ltd | Method and apparatus for removing metal from drainage |
| CN102311190A (en) * | 2011-08-19 | 2012-01-11 | 深圳市水务(集团)有限公司 | Method for removing thallium from drinking water by enhanced conventional water treatment process |
| CN103693819A (en) * | 2014-01-02 | 2014-04-02 | 中南大学 | Thallium-containing heavy metal wastewater advanced treatment method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192977A (en) * | 2014-08-21 | 2014-12-10 | 华南理工大学 | Method for deeply removing thallium in water body through hydrodynamic cavitation assisted oxidation |
| CN104310593A (en) * | 2014-10-17 | 2015-01-28 | 紫金矿业集团股份有限公司 | Biological treatment method for thallium in pit water |
| CN104310593B (en) * | 2014-10-17 | 2016-05-04 | 紫金矿业集团股份有限公司 | A kind of method of thallium in cave effluent of carrying out a biological disposal upon |
| CN104310672A (en) * | 2014-10-27 | 2015-01-28 | 湖南净源环境工程有限公司 | Thallium-containing wastewater strongly oxidizing, coagulating, adsorbing and recovering process |
| CN104310672B (en) * | 2014-10-27 | 2016-02-24 | 湖南净源环境工程有限公司 | Waste water containing thallium Strong oxdiative coagulation and adsorption recovery process |
| CN104803509A (en) * | 2015-04-10 | 2015-07-29 | 深圳中清环境科技有限公司 | Treatment process and treatment equipment for heavy metal wastewater containing thallium |
| CN108706785A (en) * | 2018-08-10 | 2018-10-26 | 大冶有色金属有限责任公司 | A kind of mining smelting wastewater exception water quality emergency treatment device and method |
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Application publication date: 20140820 |