CN105060258A - Method for recycling alkaline leached residues through selenium fixation and mercury removal - Google Patents
Method for recycling alkaline leached residues through selenium fixation and mercury removal Download PDFInfo
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- CN105060258A CN105060258A CN201510489537.3A CN201510489537A CN105060258A CN 105060258 A CN105060258 A CN 105060258A CN 201510489537 A CN201510489537 A CN 201510489537A CN 105060258 A CN105060258 A CN 105060258A
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- selenium
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Abstract
The invention provides a method for recycling alkaline leached residues through selenium fixation and mercury removal. The method comprises steps as follows: (1) performing blank roasting on lead cakes to enable selenium and mercury to volatize, and performing cooling and dust collection to obtain enriched selenium and mercury dust; (2) adding lime to the selenium and mercury dust obtained in Step (1), performing preparation, granulation and selenium fixation and mercury removal roasting to obtain selenium fixation residues, and meanwhile, condensing flue gas to obtain mercurial soot; (3) performing alkaline leaching on the selenium fixation residues to obtain alkaline leached residues and a selenium-containing leachate, wherein alkaline liquor used for alkaline leaching is a sodium hydroxide solution with the concentration of 60-120 g/L and the leaching temperature is 95-100 DEG C; (4) returning the alkaline leached residues to Step (2) to replace partial lime or all the lime, preparing and granulating the alkaline leached residues and the selenium and mercury dust obtained in Step (1), performing selenium fixation and mercury removal roasting, and sequentially circulating the process. With the adoption of the method, the alkaline leached residues are utilized, the selenium fixation rate is up to 99%, the mercury removal rate is up to 99.5%, selenium and mercury are thoroughly separated, and the lime consumption is decreased by more than 70%.
Description
Technical field
The present invention relates to a kind of method of solid selenium demercuration alkali leached mud Returning utilization, belong to the recycling of solid waste.
Background technology
In nonferrous smelting industry copper metallurgy process, during flue gas acid preparing, cigarette ash is wherein got off by dynamic wave scrubbing, to obtain purer sulfur dioxide flue gas.The hazardous solid wastes such as the cigarette ash collected and Copper smelting dust, black copper mud, arsenic filter cake are referred to as plumbous filter cake.Plumbous filter cake contains the dangerous harmful elements such as lead, zinc, copper, arsenic, mercury, selenium, as unreasonable disposal, very easily causes environmental protection accident.In existing treatment process, Gu the leaching of selenium slag adopts the method for Ore Leaching mostly, leaching yield is low, produce leached mud and generally directly store up or landfill, the selenium in leached mud can not be reclaimed, also can cause the pollution of environment.
Summary of the invention
The technical problem that the present invention solves is, the solid selenium slag of the solid selenium demercuration roasting output of selenium mercury dirt also contains Se1.5 ~ 2.5%, CaO48 ~ 55% in leached mud after alkali leaches.Selenium is wherein reclaimed, calcium oxide is utilized again.
Technical scheme of the present invention is, provides a kind of method of solid selenium demercuration alkali leached mud Returning utilization, comprises the following steps: blank for plumbous filter cake roasting makes selenium, mercury volatilize by (1), obtains the selenium mercury dirt of enrichment after cooling is gathered dust; (2) add lime in the selenium mercury dirt obtained in step (1), through batching, granulate, carry out the roasting of solid selenium demercuration, obtain solid selenium slag, flue gas obtains mercurial soot through condensation simultaneously; (3) solid selenium slag obtains alkali leached mud and the leach liquor containing selenium after alkali leaches; The alkali lye of the use that described alkali leaches for concentration be the sodium hydroxide solution of 60 ~ 120g/L, extraction temperature is 95 ~ 100 DEG C; (4) returned by described alkali leached mud in step (2) and replace part or all of lime, the selenium mercury dirt obtained with step (1) is prepared burden, is granulated, and carries out the roasting of solid selenium demercuration, circulates according to this.
Further, in step (1), the temperature of described blank roasting is 800 ~ 850 DEG C, and the time of blank roasting is 1.5 ~ 2.5h.
Further, in step (2), the condition of described solid selenium demercuration roasting is: at 600 ~ 650 DEG C, keep 60 ~ 90min.
Further, in step (3), during described alkali leaches, liquid-solid ratio is (3 ~ 7): 1, and extraction time is 3 ~ 6h.
Further, in step (2), the lime adding amount of preparing burden with selenium mercury dirt is 1.2 ~ 1.3 times of its theoretical molar requirement.
Further, when alkali leached mud return in step (2) replace part lime time, the mass ratio of the lime added in alkali leached mud and step (2) is (3 ~ 9): 1; When replacing whole lime during alkali leached mud returns step (2), in the alkali leached mud of preparing burden with selenium mercury dirt, the add-on of calcium oxide is 1.2 ~ 1.3 times of its theoretical molar requirement.
Further, described leach liquor uses SO after sulfuric acid conversion
2reduction, obtains thick selenium.
Further, before step (1), first for plumbous filter cake drying is less than 5% to water ratio, then makes-400 object quality of material account for more than 67.7% through fragmentation.
The chemical reaction that the roasting of above-mentioned steps empty is carried out, its principal reaction formula is:
Hg
2Cl
2→Hg
2Cl
2↑
HgS+O
2→Hg↑+SO
2↑
Cu
2Se+2O
2→CuSeO
3+CuO
2HgSe+3O
2→2HgO↑+2SeO
2↑
2PbSe+3O
2→2PbO+2SeO
2↑
Ag
2Se+3O
2→2Ag
2SeO
3
Ag
2Se+O
2→2Ag+SeO
2↑
Se+O
2→SeO
2↑
After adding lime in above-mentioned steps, Gu the chemical reaction that selenium demercuration carries out, its principal reaction formula is:
HgS+O
2→Hg↑+SO
2↑
HgSe+O
2+CaO→Hg↑+CaSeO
3
3HgSe+2CaO→3Hg↑+2CaSe+CaSeO
3
2MeSe+2CaO+3O
2→2MeO+2CaSeO
3
Se+O
2+CaO＝CaSeO
3
Gu selenium slag, after leaching, after leach liquor adds sulfuric acid conversion, adds SO
2precipitate reduction obtains thick selenium.The grade of thick selenium is Se >=88%.Its chemical equation is mainly:
2NaOH+CaSeO
3＝Na
2SeO
3+Ca(OH)
2
Na
2SeO
3+H
2SO
4＝Na
2SO
4+H
2SeO
3
H
2SeO
3+2Na
2O·SO2＝Se↓+H
2O+2Na
2SO
4
Or H
2seO
3+ 2SO
2+ H
2o=Se ↓+2H
2sO
4
Alkali leached mud returns the solid selenium demercuration roasting of selenium mercury dirt, and its chemical equation is:
HgS+O
2→Hg↑+SO
2↑
HgSe+O
2+CaO→Hg↑+CaSeO
3
3HgSe+2CaO→3Hg↑+2CaSe+CaSeO
3
2MeSe+2CaO+3O
2→2MeO+2CaSeO
3
Se+O
2+CaO＝CaSeO
3
The invention has the beneficial effects as follows, the present invention contains the blank roasting of high temperature, cooling is gathered dust, the solid selenium demercuration roasting of selenium mercury dirt, solid selenium slag alkali leaches, alkali leached mud returns solid selenium demercuration, leach liquor reclaims the operations such as selenium, technical process is simple, and the selenium mercury rate of recovery is high.The calcium oxide in alkali leached mud is utilized to generate CaSeO with selenium generation chemical reaction at a certain temperature
3principle, alkali leached mud is utilized, and the selenium simultaneously in leached mud is through roasting, alkali after leaching again recyclable more than 94%, and the method can save lime consumption amount more than 70%; Gu selenium rate can reach 99%, mercury removal rate can reach 99.5%, and selenium mercury is separated thoroughly.
Embodiment
Below in conjunction with embodiment, the present invention is described further.Wherein, all in the present invention percentage ratio (%) all refers to mass percent; In liquid-solid ratio, the unit of liquid is L, and the unit of solid is kg.
Embodiment 1
The prevailing quality of plumbous filter cake consists of: Se18.2%, Hg1.37%, As0.23%, Cu9.25%, Pb33.7%, Bi1.54%, all the other are the impurity such as Cl, I, Zn, S.
Plumbous filter cake gathers dust through cooling after roasting 2h at temperature is 800 ~ 850 DEG C, and obtain selenium mercury dirt, selenium mercury dirt consists of Se45%, Hg7.84%, As0.1%, Cu0.78%, Pb0.586%, Bi0.04%, and surplus is impurity.
Get selenium mercury dirt 200g, add lime 180g (lime is 63.25% containing CaO) and granulate, Gu the roasting of selenium demercuration keeps 60 ~ 90min at 600 ~ 650 DEG C.
Gu obtain solid selenium slag 333g after the roasting of selenium demercuration, containing Se26.8%, Hg0.022%, Gu selenium rate is 99.16%, demercuration rate is 99.53%.
Get solid selenium slag 300g, extraction time 4h under the condition of liquid-solid ratio 5 ︰ 1, extraction temperature 100 DEG C, hydroxide add-on 80g/L, obtains alkali leached mud 228g, and the main component of alkali leaching slag is: Se:1.56%, Hg:0.08%, CaO:51.01%; Obtain containing selenium leach liquor 2000mL, wherein containing selenium 38.85g/L, selenium leaching yield is 96.64%.
Get after 2000ml leach liquor adds sulfuric acid conversion and use SO
2reduction, thick selenium 81g, the Se grade of output is 94.1%.The deposition rate of selenium is 98.1%.
Get selenium mercury dirt 200g and add alkali leached mud 223g (Se:1.56%, CaO:51.01%) granulation, Gu obtain solid selenium slag 402g after the roasting of selenium demercuration, containing Se23.1%, Hg0.007%, Gu selenium rate is 99.34%, demercuration rate > 99.5%.
Embodiment 2
The prevailing quality of plumbous filter cake consists of: Se21.93%, Hg0.443%, Cu1.308%, Pb52.46%, Bi1.49%, all the other are the impurity such as Cl, I, Zn, S.
Plumbous filter cake gathers dust through cooling after roasting 2h at temperature is 800 ~ 850 DEG C, and obtain selenium mercury dirt, selenium mercury dirt consists of Se57.1%, Hg8.92%, As0.048%, Cu0.32%, Pb0.2%, Bi0.02%, and surplus is impurity.
Get selenium mercury dirt 10kg, add lime 11.5kg (lime is 63.25% containing CaO) and granulate, return the roasting of selenium demercuration and keep 60 ~ 90min at 600 ~ 650 DEG C.
Gu obtain solid selenium slag 20.1kg after the roasting of selenium demercuration, containing Se28.01%, Hg0.024%, Gu selenium rate is 98.6%, demercuration rate is 99.5%.
Get solid selenium slag 20kg, extraction time 4h under the condition of liquid-solid ratio 5 ︰ 1, extraction temperature 95 DEG C, hydroxide add-on 120g/L, obtains alkali leached mud 12.8kg, and the main component of alkali leaching slag is: Se:2.31%, Hg:0.04%, CaO:50.8%; Obtain containing selenium leach liquor 130L, wherein containing selenium 40.65g/L, selenium leaching yield is 94.7%.
Get after 130L leach liquor adds sulfuric acid conversion and use SO
2reduction, thick selenium 5676g, the Se grade of output is 90.4%.The deposition rate of selenium is 97.1%.
Get selenium mercury dirt 10kg and add alkali leached mud 11.5kg (wherein Se:2.31%, CaO:50.8%) and lime 2.3kg (wherein CaO:63.25%) granulate, Gu obtain solid selenium slag 21.4kg after the roasting of selenium demercuration, containing Se27.5%, Hg0.019%, Gu selenium rate is 98.5%, demercuration rate > 99.5%.
Claims (8)
1. a method for solid selenium demercuration alkali leached mud Returning utilization, is characterized in that, comprise the following steps:
(1) selenium, mercury are volatilized blank for plumbous filter cake roasting, after cooling is gathered dust, obtain the selenium mercury dirt of enrichment;
(2) add lime in the selenium mercury dirt obtained in step (1), through batching, granulate, carry out the roasting of solid selenium demercuration, obtain solid selenium slag, flue gas obtains mercurial soot through condensation simultaneously;
(3) solid selenium slag obtains alkali leached mud and the leach liquor containing selenium after alkali leaches; The alkali lye of the use that described alkali leaches for concentration be the sodium hydroxide solution of 60 ~ 120g/L, extraction temperature is 95 ~ 100 DEG C;
(4) returned by described alkali leached mud in step (2) and replace part or all of lime, the selenium mercury dirt obtained with step (1) is prepared burden, is granulated, and carries out the roasting of solid selenium demercuration, circulates according to this.
2. the method for claim 1, is characterized in that, in step (1), the temperature of described blank roasting is 800 ~ 850 DEG C, and the time of blank roasting is 1.5 ~ 2.5h.
3. the method for claim 1, is characterized in that, in step (2), the condition of described solid selenium demercuration roasting is: at 600 ~ 650 DEG C, keep 60 ~ 90min.
4. the method for claim 1, is characterized in that, in step (3), during described alkali leaches, liquid-solid ratio is (3 ~ 7): 1, and extraction time is 3 ~ 6h.
5. the method for claim 1, is characterized in that, in step (2), the lime adding amount of preparing burden with selenium mercury dirt is 1.2 ~ 1.3 times of its theoretical molar requirement.
6. the method for claim 1, is characterized in that, when alkali leached mud return in step (2) replace part lime time, the mass ratio of the lime added in alkali leached mud and step (2) is (3 ~ 9): 1; When replacing whole lime during alkali leached mud returns step (2), in the alkali leached mud of preparing burden with selenium mercury dirt, the add-on of calcium oxide is 1.2 ~ 1.3 times of its theoretical molar requirement.
7. the method for claim 1, is characterized in that, described leach liquor uses SO after sulfuric acid conversion
2reduction, obtains thick selenium.
8. the method for claim 1, is characterized in that, before step (1), first for plumbous filter cake drying is less than 5% to water ratio, then makes-400 object quality of material account for more than 67.7% through fragmentation.
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|---|---|---|---|
| CN201510489537.3A CN105060258B (en) | 2015-08-11 | 2015-08-11 | A kind of method of solid selenium demercuration alkali leached mud Returning utilization |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959274A (en) * | 2022-06-01 | 2022-08-30 | 紫金铜业有限公司 | Method for efficiently separating valuable elements in lead filter cake |
| CN115537550A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for efficiently separating and recovering mercury and selenium in acid mud through microwave heating and alkaline oxidation |
| CN116443821A (en) * | 2023-03-21 | 2023-07-18 | 葫芦岛锌业股份有限公司 | Method for producing selenium-rich fertilizer additive by using selenate mud |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964402A (en) * | 2013-02-06 | 2014-08-06 | 安徽省思达新材料科技有限公司 | Method for utilizing solid industrial waste containing trace selenium to extract high-purity selenium for new materials |
| CN104498722A (en) * | 2014-12-16 | 2015-04-08 | 贵州重力科技环保有限公司 | Method for comprehensively recovering mercury and selenium from metallurgical slag |
-
2015
- 2015-08-11 CN CN201510489537.3A patent/CN105060258B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964402A (en) * | 2013-02-06 | 2014-08-06 | 安徽省思达新材料科技有限公司 | Method for utilizing solid industrial waste containing trace selenium to extract high-purity selenium for new materials |
| CN104498722A (en) * | 2014-12-16 | 2015-04-08 | 贵州重力科技环保有限公司 | Method for comprehensively recovering mercury and selenium from metallurgical slag |
Non-Patent Citations (1)
| Title |
|---|
| 徐盛明等: ""从汞硒物料中回收汞和硒"", 《《有色金属(冶炼部分)》》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959274A (en) * | 2022-06-01 | 2022-08-30 | 紫金铜业有限公司 | Method for efficiently separating valuable elements in lead filter cake |
| CN114959274B (en) * | 2022-06-01 | 2024-02-13 | 紫金铜业有限公司 | Method for efficiently separating valuable elements in lead filter cake |
| CN115537550A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for efficiently separating and recovering mercury and selenium in acid mud through microwave heating and alkaline oxidation |
| CN115537550B (en) * | 2022-11-29 | 2023-03-17 | 昆明理工大学 | Method for efficiently separating and recovering mercury and selenium in acid mud by microwave heating in cooperation with alkaline oxidation |
| CN116443821A (en) * | 2023-03-21 | 2023-07-18 | 葫芦岛锌业股份有限公司 | Method for producing selenium-rich fertilizer additive by using selenate mud |
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| CN105060258B (en) | 2017-05-31 |
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