CN1067229A - Treatment method of thallium-containing waste water - Google Patents

Treatment method of thallium-containing waste water Download PDF

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CN1067229A
CN1067229A CN 92105763 CN92105763A CN1067229A CN 1067229 A CN1067229 A CN 1067229A CN 92105763 CN92105763 CN 92105763 CN 92105763 A CN92105763 A CN 92105763A CN 1067229 A CN1067229 A CN 1067229A
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thallium
add
waste water
coprecipitator
wastewater treatment
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CN 92105763
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CN1026480C (en
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梁保胜
马启明
吕素秀
杨德华
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BEIJING NUCLEAR INSTR FACTORY
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BEIJING NUCLEAR INSTR FACTORY
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Abstract

The invention relates to a method for precipitation treatment of thallium-containing wastewater, which comprises adjusting the pH of the wastewater to 2-5 with acid, and then using oxidant (NaClO, H)2O2,Br2Water, chlorine) to oxidize the monovalent thallium in the wastewater into trivalent thallium, and then adding a coprecipitator and hydroxyl to precipitate the thallium, thereby removing the thallium in the wastewater. The method has the advantages of simple flow, easy operation, low cost, no introduction of other harmful impurities and good thallium removal effect.

Description

The treatment process of waste water containing thallium
The present invention relates to a kind of wastewater treatment method, more particularly, is a kind of treatment process of waste water containing thallium.
Thallium and thallium compound are highly toxic substances, are producing NaI(Tl) can produce thallic waste water in the crystal, its thallium-containing quantity is generally 2~15mg/l, in addition have reach 100mg/ml.The strictest standard (as mercury) according to the toxic heavy metal discharge of wastewater of China regulation should be≤0.05mg/l.Therefore, the thallium-containing quantity of waste water containing thallium has substantially exceeded this standard.In order to prevent and avoid the pollution of waste water containing thallium, must reduce the thallium content in the waste water containing thallium, to reach emission standard to environment.
At present, the method for separation thallium has ion exchange method, extraction process, spontaneous evaporation method and the precipitator method.Ion exchange method needs wash-out, and the concentrated solution behind the wash-out is also needed further to handle.Extraction process has extraction and reextraction process, and the concentrated solution that back extraction is taken out also needs further to handle, and its process is complicated.The spontaneous evaporation method is taken up an area of many, and waste water containing thallium exposes to the open air again outside, to the neither safety of people and animals.The precipitator method are all simple than aforesaid method, two kinds of its branch organic deposition and inorganic precipitations.The used precipitation agent price of organic deposition method is expensive, should not do the processing of industrial waste water containing thallium, and these reagent have thiocarbamide, thionalide, thiooxine, tropeolin-D, quadrol, Tetraphenyl sodium borate ... Deng.The inorganic precipitation method has sulfonium ion precipitation thallium, and (" Removal of metals from wastewater.Neutralization and Precipitation ", Cushnic.G.C.1984), it is better that this method is removed the thallium effect, because Tl S solubility product is 5 * 10 -21, the precipitation agent price is also cheap, but this method adds sulphur, and sulphur content>1mg/l in processed waste water still can not discharge at last, otherwise needs further sulphur removal.
The object of the invention provides a kind of objectionable impurities of not introducing, and removes the treatment process of the effective waste water containing thallium of thallium.
The present invention implements like this.Adopt Tl(OH) 3The precipitator method.Tl(OH) 3Be insoluble compound, its solubility product is 6.3 * 10 -46Thallium in nature and the waste water is Tl +Be the precipitation thallium, need thallium is oxidized to Tl 3+, Tl +→ Tl 3+Standard oxidationreduction potential E 0=1.26, as long as the strong E of oxidisability of oxygenant 0>1.26, just can be with Tl +→ Tl 3+But handle as industrial useless thallium liquid, the oxygenant of adding must be inexpensive, be easy to get, be suitable for, available oxygenant has NaClO, Cl 2, hydrogen peroxide, bromine water ... Deng.Before adding oxygenant, to make earlier to contain the acidifying of thallium liquid and reoxidize, be shown below:
Used acid is mineral acid, and H is arranged 2SO 4, HNO 3, HCl.Treat Tl 3+After the generation, add alkali, promptly generate Tl(OH) 3Precipitation.For making Tl(OH) 3Precipitate fully, the adding coprecipitator of still needing, the coprecipitator that is added also must cheaply be easy to get, and at first is Ca 2+, secondly be Al 3+, as CaCl 2, Ca(OH) 2, AlCl 36H 2O, NH 3Al(SO 4) 212H 2O, KAl(SO 4) 212H 2O, Al 2(SO 4) 318H 2O etc.The precipitation agent that adds can be NaOH, NH 3OH.The add-on of oxygenant in molar weight, should be Tl +More than 15 times for well, when thallium-containing quantity in the waste water≤40mg/l, the NaClO liquid measure of the nearly saturated chlorine of adding is 0.5~2ml/l, the acid amount of adding gets final product with pH=2~5.The co-precipitation dosage that adds is 0.5~1g/l.When thallium content is high again in the waste water, then add the corresponding increase of amount of reagent.To fully stir when adding acid, oxygenant, coprecipitator, oxidation is fully finished.The alkali number that adds adds the kind of coprecipitator successively and decides, when coprecipitator is Ca 2+The time, then the add-on of alkali is as the criterion with pH value of solution 〉=11, and coprecipitator is Al 3+The time, be as the criterion with pH=7~8.
Method of the present invention is carried out as follows:
(1) in waste water containing thallium, add mineral acid, transfer pH to 2-5,
(2) add oxygenant, chlorine bleach liquor (NaClO), hydrogen peroxide (H are arranged 2O 2), bromine water or chlorine.The amount that adds NaClO liquid or hydrogen peroxide is 0.5~1ml/l, and the bromine water amount is deep yellow with waste water and is as the criterion, and feeds amount of chlorine and is as the criterion clearly with solution becomes.
(3) add coprecipitator Ca 2+Or Al 3+, add-on is 0.5~1g/l.
(4) add alkali, making pH=7~8(work as coprecipitator is Al 3+The time), or 〉=11(when coprecipitator be Ca 2+The time).
(5) precipitated liquid was placed 1~6 hour or was spent the night, and removed precipitation, and supernatant liquor is the waste water except that thallium, can discharge.
Through the waste water containing thallium of above-mentioned processing, its thallium-containing quantity≤0.05mg/l reaches country fully and allows emission standard, and does not introduce the objectionable impurities of environmental pollution in waste water.
Embodiment 1.(1) is the waste water 250l of 9.68mg/l with thallium-containing quantity, pumps in the treatment trough, add H 2SO 4, make pH=3, stir,
(2) the NaClO liquid 250l of the nearly saturated chlorine of adding stirs,
(3) add CaCl 2150g stirred 30 minutes,
(4) add NaOH,, stirred 30 minutes to pH=12,
(5) placed liquid, discharging supernatant liquor, filtering Tl(OH) 3, Ca(OH) 2And Mg(OH) 2Co-precipitation pending.
Supernatant liquor by analysis, its thallium-containing quantity is 0.011mg/l.
Embodiment 2.
(1) is that the waste water 250l of 36mg/l pumps in the treatment trough with thallium-containing quantity, adds H 2SO 4Make pH=3, stir,
(2) the NaClO liquid 400ml of the nearly saturated chlorine of adding stirs,
(3) add CaCl 2150g stirred 30 minutes,
(4) add NaOH and make pH=12, stirred 1.5 hours, Tl(OH) 3Precipitation is complete,
(5) place the filtration of spending the night, discharging supernatant liquor, filtering Tl(OH) 3, Ca(OH) 2And Mg(OH) 2Co-precipitation pending.
Supernatant liquor by analysis, its thallium-containing quantity is 0.013mg/l.
Embodiment 3.
(1) is that the waste water 250l of 8mg/l pumps in the treatment trough with thallium-containing quantity, adds H 2SO 4Make pH=3, stir,
(2) the NaClO liquid 250ml of the nearly saturated chlorine of adding stirs,
(3) add AlCl 36H 2O 130 grams stirred 30 minutes,
(4) add NaOH and make pH=7.5, stirred 1.5 hours,
(5) precipitation solution is placed the filtration of spending the night, the discharging supernatant liquor, and the filtering co-precipitation is pending.
Supernatant liquor is analyzed, and thallium-containing quantity is 0.012mg/l.
Embodiment 4.
(1) is that the waste water 250l of 9.3mg/l pumps in the treatment trough with thallium-containing quantity, under agitation adds H 2SO 4Make pH=2.5,
(2) add nearly saturated NaClO liquid 250ml, stir,
(3) add NH 3AlSO 412H 2O 100g stirred 30 minutes,
(4) add NH 4OH makes pH=7.5,
(5) precipitated liquid was placed 7 hours, filter, and the discharging supernatant liquor, it is pending to remove filter residue.
Supernatant liquor by analysis, thallium-containing quantity is 0.011mg/l.
Embodiment 5.
(1) is the waste water 250l of 6.8mg/l with thallium-containing quantity, pumps in the treatment trough, under stirring state, add H 2SO 4, transfer pH=2,
(2) add 30% hydrogen peroxide 120ml, stir,
(3) add AlCl 36H 2O 120g stirred 30 minutes,
(4) add NaOH and transfer pH=7.2, stirred 1 hour,
(5) the precipitated liquid age overnight filters, the discharging supernatant liquor, and it is pending to remove filter residue.
Clear liquid analytically, thallium-containing quantity is 0.01mg/l.
Embodiment 6.
(1) is in the 10l waste water of 16mg/l at thallium-containing quantity, adds H 2SO 4, make pH=2.5, stir,
(2) add bromine water and make solution be deep yellow, stir,
(3) add KAlSO 412H 2O 6g, stirring dissolves,
(4) add NaOH solution and make pH=7.2,
(5) precipitated liquid was placed after 6 hours, filter, and the discharging supernatant liquor, it is pending to remove filter residue.
Clear liquid analytically, thallium-containing quantity is 0.005mg/l.
Embodiment 7.
(1) in being the waste water of 20.5mg/l, 20l thallium content adds H 2SO 4, make pH=5, stir,
(2) feeding chlorine is clear to solution becomes, stir,
(3) add CaCl 210g stirs,
(4) add NaOH, transfer pH=11.5, stir,
(5) precipitated liquid is placed the filtration of spending the night, the discharging supernatant liquor, and it is pending to remove filter residue.
Clear liquid analytically, thallium-containing quantity is 0.0005mg/l.
From above-mentioned numerous embodiment, the inventive method is simple and easy, and is easy and simple to handle, required reagent is cheap, convenient sources, and gained is ideal as a result, thallium-containing quantity all reaches state emission standard, and (13 μ g/l are for to various biological standards also to have reached the standard of American National environment provided waters thallium content; 48 μ g/l are for to the hydrobiont standard).

Claims (5)

1, a kind of treatment process of waste water containing thallium, this method are to remove thallium with the precipitator method, it is characterized in that carrying out as follows:
(1) in waste water containing thallium, add mineral acid, transfer pH to 2~5,
(2) adding makes Tl +→ Tl 3+Redox potential E 0>1.26 oxygenant,
(3) add Ca 2+Or Al 3+Coprecipitator,
(4) (coprecipitator is Al to add adjusting PH with base to 7~8 3+The time) or 〉=11 (precipitation agent is Ca 2+The time),
(5) precipitated liquid is placed 1~6 hour or the filtration of spending the night, and the discharging supernatant liquor is removed filter residue.
2, method of wastewater treatment as claimed in claim 1 is characterized in that the mineral acid that adds in the step (1) is H 2SO 4, HCl, HNO 3
3, method of wastewater treatment as claimed in claim 1 is characterized in that the oxygenant in the step (2) is NaClO, H 2O 2, bromine water, chlorine, NaClO liquid or H 2O 2Add-on is 15 times (molar weight meters) of thallium, and the bromine water add-on is deep yellow with exhausted water and is as the criterion, and the chlorine add-on is as the criterion clearly with the waste water change.
4, method of wastewater treatment as claimed in claim 1 is characterized in that adding coprecipitator in the step (3) is CaCl 2, Ca(OH) 2, AlCl 3, NH 3AlSO 412H 2O, KAlSO 412H 2O, Al 2(SO 4) 318H 2O.
5, method of wastewater treatment as claimed in claim 1 is characterized in that the alkali that adds in the step (4) is NaOH, NH 3(OH).
CN 92105763 1992-07-15 1992-07-15 Treatment method of thallium-containing waste water Expired - Fee Related CN1026480C (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301219C (en) * 2005-10-08 2007-02-21 广州大学 Treatment of thallium and heavy metal containing mixed waste water drained by sulfuric acid plant
CN102107969A (en) * 2011-01-21 2011-06-29 广州市自来水公司 Method for emergently treating thallium-polluted raw water
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
CN102320700A (en) * 2011-08-12 2012-01-18 东莞市东江水务有限公司 Method for removing thallium pollution in source water of drinking water
CN104773878A (en) * 2015-04-28 2015-07-15 韶关朗润环保科技有限公司 Method for removing trace of thallium in sewage
CN104773863A (en) * 2015-02-13 2015-07-15 湖南永清环保研究院有限责任公司 Deep purification process for thallium-containing waste water
CN105060557A (en) * 2015-07-31 2015-11-18 广州大学 New method for simultaneously and efficiently removing thallium and arsenic from smelting wastewater
CN107904400A (en) * 2017-12-13 2018-04-13 清远先导材料有限公司 The separation and recovery method of thallium in a kind of sulfuric acid nickel and cobalt solution
CN108380395A (en) * 2018-02-28 2018-08-10 湘潭大学 A kind of lead thallium separation method of the concentrate of lead sulfide ore containing thallium
CN109626414A (en) * 2019-01-31 2019-04-16 广州大学 A method of thallium and rhenium being recycled in waste acid from smelting
CN110194538A (en) * 2018-02-24 2019-09-03 湖南金蓝田环保工程有限公司 A method of the coordination grafting advanced treating of heavy metal wastewater thereby containing thallium
CN110252270A (en) * 2019-07-05 2019-09-20 广东华准检测技术有限公司 A kind of desorption cycle of the titanium peroxide containing thallium utilizes method and device
CN111719046A (en) * 2020-04-02 2020-09-29 桂林理工大学 Method for separating thallium from water body and recovering extractant

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CN1317205C (en) * 2005-05-30 2007-05-23 广州大学 Treating method for waste water containing thallium
CN102768191B (en) * 2012-07-31 2014-06-18 浙江中一检测研究院股份有限公司 Method for easily detecting trace thallium in water
CN105293775A (en) * 2015-11-19 2016-02-03 湖南力泓新材料科技股份有限公司 Method adopting combined technology of pre-oxidation and coagulating sedimentation to process wastewater containing thallium and ammonia-nitrogen

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301219C (en) * 2005-10-08 2007-02-21 广州大学 Treatment of thallium and heavy metal containing mixed waste water drained by sulfuric acid plant
CN102107969A (en) * 2011-01-21 2011-06-29 广州市自来水公司 Method for emergently treating thallium-polluted raw water
CN102320700A (en) * 2011-08-12 2012-01-18 东莞市东江水务有限公司 Method for removing thallium pollution in source water of drinking water
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
CN104773863A (en) * 2015-02-13 2015-07-15 湖南永清环保研究院有限责任公司 Deep purification process for thallium-containing waste water
CN104773878A (en) * 2015-04-28 2015-07-15 韶关朗润环保科技有限公司 Method for removing trace of thallium in sewage
CN105060557A (en) * 2015-07-31 2015-11-18 广州大学 New method for simultaneously and efficiently removing thallium and arsenic from smelting wastewater
CN107904400A (en) * 2017-12-13 2018-04-13 清远先导材料有限公司 The separation and recovery method of thallium in a kind of sulfuric acid nickel and cobalt solution
CN107904400B (en) * 2017-12-13 2019-09-03 清远先导材料有限公司 The separation and recovery method of thallium in a kind of sulfuric acid nickel and cobalt solution
CN110194538A (en) * 2018-02-24 2019-09-03 湖南金蓝田环保工程有限公司 A method of the coordination grafting advanced treating of heavy metal wastewater thereby containing thallium
CN108380395A (en) * 2018-02-28 2018-08-10 湘潭大学 A kind of lead thallium separation method of the concentrate of lead sulfide ore containing thallium
CN109626414A (en) * 2019-01-31 2019-04-16 广州大学 A method of thallium and rhenium being recycled in waste acid from smelting
CN109626414B (en) * 2019-01-31 2021-06-08 广州大学 Method for recovering thallium and rhenium from smelting waste acid
CN110252270A (en) * 2019-07-05 2019-09-20 广东华准检测技术有限公司 A kind of desorption cycle of the titanium peroxide containing thallium utilizes method and device
CN110252270B (en) * 2019-07-05 2022-04-19 生态环境部华南环境科学研究所 Desorption recycling method and device for thallium-containing titanium peroxide
CN111719046A (en) * 2020-04-02 2020-09-29 桂林理工大学 Method for separating thallium from water body and recovering extractant

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