CN104944623A - Novel method for removing thallium from zinc-sulfate-production mother water and zinc carbonate washing water - Google Patents
Novel method for removing thallium from zinc-sulfate-production mother water and zinc carbonate washing water Download PDFInfo
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- CN104944623A CN104944623A CN201510011110.2A CN201510011110A CN104944623A CN 104944623 A CN104944623 A CN 104944623A CN 201510011110 A CN201510011110 A CN 201510011110A CN 104944623 A CN104944623 A CN 104944623A
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- thallium
- zinc
- washing water
- sulfide
- precipitation
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Abstract
The invention relates to a novel method for removing thallium from zinc-sulfate-production mother water and zinc carbonate washing water, which comprises the following steps: sucking thallium-containing wastewater from a wastewater storage tank into a pH regulating kettle, adding sulfuric acid from a metering tank to regulate the pH value to 3.9, sucking into a treatment kettle, adding a 30% sodium sulfide solution according to the principle of adding 0.6kg of sodium sulfide to every 1M<3> of thallium-containing wastewater, sufficiently and uniformly mixing under the action of stirring to generate a thallium sulfide precipitate, putting into a sloping plate precipitation tank, adding a flocculant to quickly precipitate, implementing liquid-solid separation under the action of the sloping plate, drying the solid by a high-density filter, sending the filtering water into an S drainage tank to be discharged along with the supernate after reaching the standard, and sending the filter residue (containing thallium sulfide and other metal sulfides) to a smeltery to perform smelting and recover thallium. Compared with the existing oxidation process, chlorination process and iodination process, the method provided by the invention has the advantages of thorough thallium precipitation, simple equipment, investment saving, low operating cost and the like.
Description
Technical field
The present invention relates to except the method for thallium in a kind of chemical process, particularly a kind of novel method from producing except thallium the mother liquid coming of zinc sulfate and zinc carbonate washing water.
Background technology
Existing plumbous in smelting, in smelting zinc and wet method electrolytic zinc process except thallium (thallous sulfate) method, mostly adopt oxidation style, iodination or replace plumbous cadmium and add zinc powder and plumbous cadmium coprecipitation method, although these three kinds of methods can remove thallium to a certain extent, but exist except the halfway deficiency of thallium, be difficult to reach the environmental requirement of thallium content under 0.01ug ∕ L, and cost of disposal is high (see " a kind of with Pb-Zn deposits smelting wastewater for the method for Thallous iodide prepared by raw material " that Guangzhou University contriver Chen Yong is prosperous etc., " the removing the method for thallium from zinc-containing solution " of Espoo, Finland Outokumpu OY).
Summary of the invention
An object of the present invention overcomes the deficiencies in the prior art, and provide the novel method except thallium a kind of mother liquid coming from production zinc sulfate and zinc carbonate washing water, not only except thallium is effective, can also remove other metal-salt simultaneously, reach the object of purification.
The technical scheme realizing above-mentioned purpose of the present invention is: a kind of novel method from producing except thallium the mother liquid coming of zinc sulfate and zinc carbonate washing water, comprises following processing step:
First by reservoir containing thallium, produce the mother liquid coming of zinc sulfate and zinc carbonate washing water suction pH regulator pond, put into after sulfuric acid is adjusted to pH3.8-4.5 again from scale tank, in suction process still, add sodium sulfide solution, under the effect of stirring, allow sodium sulphite and sulfuric acid produce gentleness and react (Na
2s+H
2sO
4=Na
2sO
4+ H
2s ↑), monovalent salt and/or the divalent salts of the various metals such as the hydrogen sulfide produced under hydraulic pressure effect and thallium, zinc, lead, cadmium react, and generate sulfide and separate out precipitation (2Tl+H
2s=Tl
2s ↓), the pH value of liquid increases gradually simultaneously, and thallous sulfate produces replacement(metathesis)reaction with sodium sulphite again, forms Thallous sulfide Precipitation (Tl
2sO
4+ Na
2s=Tl
2s ↓+Na
2sO
4), after thallium is separated out completely, mixed solution is put into flocculation basin together with throw out, rapid precipitation under flocculation agent hydrophilic interaction, swash plate is separated supernatant water, and throw out filters through highly dense filter, its filtered water and supernatant water return multiplexing or discharge, the dry slag (Tl of filtration
2the solids such as S, ZnS, CdS, pbS) deliver to smeltery and be used as raw material or send special landfill yard to bury.
The further technical scheme of the present invention is: by regulate pH containing after in thallium washing water suction process still, add the ratio of sodium sulphite 0.5-2kg in 1M3 containing thallium washing water, add sodium sulfide solution.
The present invention further technical scheme is: the sodium sulfide solution added is the sodium sulfide solution of Containing Sulfur sodium 30-40%.
The present invention is owing to have selected specific current potential pH value (3.8-4.5), from other adopt sulfuration method to have fundamentally different, because it is when acidity is slightly strong (pH3.8-4.5), gentle hydrogen sulfide can be produced, under hydraulic pressure effect, hydrogen sulfide is not volatile, effectively can reach and force transition to be collided with thallium salt, enter mat woven of fine bamboo strips vulcanization reaction climax, reach Thallous sulfide and generate precipitation precipitation fast; Along with alkaline substance sodium sulphite in water, under H ionization, pH rises to 5-5.5 time, be applicable to the precipitation that Na2S and TI2S04 metathesis generates TI2S, the thallium salt that first time fails to precipitate effectively is implemented mat woven of fine bamboo strips secondary precipitation precipitation, thallium and other metal-salt in water is made to reach the object of thoroughly precipitation purification, compared with prior art, there is following features:
1, except thallium is effective, thoroughly can remove the thallium in the mother liquid coming and zinc carbonate washing water producing zinc sulfate, and other metal-salt can be removed simultaneously, reach purification object;
2, the scavenging agent amount of sodium sulfide used is little, and 1M3 water only uses 0.5-2kg, 50 ℅s fewer than potassium iodide method, potassium permanganate hydrogen peroxide oxidation, and the few half of low price, operation cost of disposal is low;
3, technique is simple, flow process is short, production process is easy to control, reduced investment;
4, secondary sedimentation can be completed in same still, solid-liquor separation can be completed again in same settling tank, thus facility investment is saved, by 10,000 ten thousand tons of zinc carbonate throughput, produce waste water containing thallium treatment facility to drop into compared with prior art equipment investment, 3,000,000 yuan can be saved, and make thallium and other metal-salt in water thoroughly precipitate purification.
Below in conjunction with embodiment, detailed content of the present invention is further described.
Embodiment
Embodiment 1
Except a novel method for thallium from the mother liquid coming and zinc carbonate washing water of production zinc sulfate, comprise following processing step:
First from waste water tank by waste water containing thallium suction pH regulator still, sulfuric acid is put into again from scale tank, after adjust ph 3.9, in suction process still, the ratio of sodium sulphite 0.6kg is added in 1M3 waste water containing thallium, add the sodium sulfide solution of 30%, fully stir evenly under the effect of stirring, make it to produce Thallous sulfide precipitation, put into inclined-plate clarifying basin and add flocculation agent by its rapid precipitation, swash plate effect is utilized to implement solid-liquor separation, solids is filtered dry through highly dense filter, its filtered water enters S blowoff basin together with supernatant liquor qualified discharge, filter residue (Containing Sulfur thallium and other metallic sulfide) is delivered to smeltery and is smelted recovery thallium etc.
Embodiment 2
Except a novel method for thallium from the mother liquid coming and zinc carbonate washing water of production zinc sulfate, comprise following processing step:
First from waste water tank by waste water containing thallium suction pH regulator still, sulfuric acid is put into again from scale tank, after adjust ph 4.1, in suction process still, the ratio of sodium sulphite 1kg is added in 1M3 waste water containing thallium, add the sodium sulfide solution of 35%, fully stir evenly under the effect of stirring, make it to produce Thallous sulfide precipitation, put into inclined-plate clarifying basin and add flocculation agent by its rapid precipitation, swash plate effect is utilized to implement solid-liquor separation, solids is filtered dry through highly dense filter, its filtered water enters S blowoff basin together with supernatant liquor qualified discharge, filter residue (Containing Sulfur thallium and other metallic sulfide) is delivered to smeltery and is smelted recovery thallium etc.
Embodiment 3
Except a novel method for thallium from the mother liquid coming and zinc carbonate washing water of production zinc sulfate, comprise following processing step:
First from waste water tank by waste water containing thallium suction pH regulator still, sulfuric acid is put into again from scale tank, after adjust ph 4.4, in suction process still, the ratio of sodium sulphite 2kg is added in 1M3 waste water containing thallium, add the sodium sulfide solution of 40%, fully stir evenly under the effect of stirring, make it to produce Thallous sulfide precipitation, put into inclined-plate clarifying basin and add flocculation agent by its rapid precipitation, swash plate effect is utilized to implement solid-liquor separation, solids is filtered dry through highly dense filter, its filtered water enters S blowoff basin together with supernatant liquor qualified discharge, filter residue (Containing Sulfur thallium and other metallic sulfide) is delivered to smeltery and is smelted recovery thallium etc.
The present invention by regulate pH containing after adding sodium sulfide solution in thallium washing water suction process still, a part of and rare weak sulfuric acid reaction generates hydrogen sulfide, and hydrogen sulfide reacts with thallium and generates Thallous sulfide and separate out, and adds flocculation agent and precipitates; A part is then thallous sulfate and the direct metathesis of sodium sulphite generates sodium sulfate and thallous sulfide precipitates, and it is then without thallium, water without other heavy metal that its supernatant liquor is discharged.
Principle of work of the present invention is: select specific current potential pH value (3.8-4.5), when acidity is slightly strong (pH3.8-4.5), gentle reaction can produce hydrogen sulfide, under hydraulic pressure effect, hydrogen sulfide is not volatile, thus effectively reach and force transition to be collided with thallium salt, enter mat woven of fine bamboo strips vulcanization reaction climax, reach Thallous sulfide and generate fast and separate out precipitation; Along with alkaline substance sodium sulphite in water, under H ionization, pH rises to 5.0-5.5 time, be applicable to Na
2s and TI
2s0
4metathesis generates TI
2the precipitation of S, effectively implements mat woven of fine bamboo strips secondary precipitation precipitation by the thallium salt that first time fails to precipitate, make thallium and other metal-salt in water reach the object of thoroughly precipitation purification.
Claims (3)
1. from the mother liquid coming and zinc carbonate washing water of production zinc sulfate, remove a novel method for thallium, it is characterized in that comprising following processing step:
First by reservoir containing thallium, produce the mother liquid coming of zinc sulfate and zinc carbonate washing water suction pH regulator pond, put into after sulfuric acid is adjusted to pH3.8-4.5 again from scale tank, in suction process still, add sodium sulfide solution, under the effect of stirring, allow sodium sulphite and sulfuric acid produce gentleness and react (Na
2s+H
2sO
4=Na
2sO
4+ H
2s ↑), monovalent salt and/or the divalent salts of the various metals such as the hydrogen sulfide produced under hydraulic pressure effect and thallium, zinc, lead, cadmium react, and generate sulfide and separate out precipitation (2Tl+H
2s=Tl
2s ↓), the pH value of liquid increases gradually simultaneously, and thallous sulfate produces replacement(metathesis)reaction with sodium sulphite again, forms Thallous sulfide Precipitation (Tl
2sO
4+ Na
2s=Tl
2s ↓+Na
2sO
4), after thallium is separated out completely, mixed solution is put into flocculation basin together with throw out, rapid precipitation under flocculation agent hydrophilic interaction, swash plate is separated supernatant water, and throw out filters through highly dense filter, its filtered water and supernatant water return multiplexing or discharge, the dry slag (Tl of filtration
2the solids such as S, ZnS, CdS, pbS) deliver to smeltery and be used as raw material or send special landfill yard to bury.
2. the novel method from producing except thallium the mother liquid coming of zinc sulfate and zinc carbonate washing water according to claim 1, it is characterized in that by regulate pH containing after in thallium washing water suction process still, add the ratio of sodium sulphite 0.5-2kg in 1M3 containing thallium washing water, add sodium sulfide solution.
3. the novel method from producing except thallium the mother liquid coming of zinc sulfate and zinc carbonate washing water according to claim 1 and 2, is characterized in that the sodium sulfide solution added is the sodium sulfide solution of Containing Sulfur sodium 30-40%.
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| CN201510011110.2A CN104944623A (en) | 2015-01-11 | 2015-01-11 | Novel method for removing thallium from zinc-sulfate-production mother water and zinc carbonate washing water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510011110.2A CN104944623A (en) | 2015-01-11 | 2015-01-11 | Novel method for removing thallium from zinc-sulfate-production mother water and zinc carbonate washing water |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060554A (en) * | 2015-07-29 | 2015-11-18 | 湖南水口山有色金属集团有限公司 | Method for removing heavy metals in zinc sulfate production wastewater |
| CN106746024A (en) * | 2017-01-24 | 2017-05-31 | 湘潭大学 | A kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium |
| CN108467133A (en) * | 2018-04-11 | 2018-08-31 | 赛恩斯环保股份有限公司 | A kind of processing method of precious metal smelting arsenic in waste water cadmium separation resource reusing |
| CN110803804A (en) * | 2019-11-27 | 2020-02-18 | 衡阳旭光锌锗科技有限公司 | Wastewater treatment system for zinc sulfate production |
| CN114735854A (en) * | 2022-04-20 | 2022-07-12 | 白银有色集团股份有限公司 | Device and method for treating thallium-containing wastewater in non-ferrous metal smelting |
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| CN102765831A (en) * | 2012-07-25 | 2012-11-07 | 中南大学 | Purification method of wastewater containing heavy metal and arsenic |
| CN103649349A (en) * | 2011-05-10 | 2014-03-19 | 凯米罗总公司 | Methods for removing contaminants from aqueous systems |
| CN103693819A (en) * | 2014-01-02 | 2014-04-02 | 中南大学 | Thallium-containing heavy metal wastewater advanced treatment method |
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2015
- 2015-01-11 CN CN201510011110.2A patent/CN104944623A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649349A (en) * | 2011-05-10 | 2014-03-19 | 凯米罗总公司 | Methods for removing contaminants from aqueous systems |
| CN102765831A (en) * | 2012-07-25 | 2012-11-07 | 中南大学 | Purification method of wastewater containing heavy metal and arsenic |
| CN103693819A (en) * | 2014-01-02 | 2014-04-02 | 中南大学 | Thallium-containing heavy metal wastewater advanced treatment method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060554A (en) * | 2015-07-29 | 2015-11-18 | 湖南水口山有色金属集团有限公司 | Method for removing heavy metals in zinc sulfate production wastewater |
| CN106746024A (en) * | 2017-01-24 | 2017-05-31 | 湘潭大学 | A kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium |
| CN108467133A (en) * | 2018-04-11 | 2018-08-31 | 赛恩斯环保股份有限公司 | A kind of processing method of precious metal smelting arsenic in waste water cadmium separation resource reusing |
| CN110803804A (en) * | 2019-11-27 | 2020-02-18 | 衡阳旭光锌锗科技有限公司 | Wastewater treatment system for zinc sulfate production |
| CN114735854A (en) * | 2022-04-20 | 2022-07-12 | 白银有色集团股份有限公司 | Device and method for treating thallium-containing wastewater in non-ferrous metal smelting |
| CN114735854B (en) * | 2022-04-20 | 2023-10-24 | 白银有色集团股份有限公司 | Device and method for treating thallium-containing wastewater in nonferrous metal smelting |
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