CN104357668A - Method of recycling valuable metals from arsenic-containing soot - Google Patents
Method of recycling valuable metals from arsenic-containing soot Download PDFInfo
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- CN104357668A CN104357668A CN201410690393.3A CN201410690393A CN104357668A CN 104357668 A CN104357668 A CN 104357668A CN 201410690393 A CN201410690393 A CN 201410690393A CN 104357668 A CN104357668 A CN 104357668A
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- slag
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention relates to a method of recycling valuable metals from arsenic-containing soot. The method comprises the following steps: (1) mixing acidic wastewater with white soot, controlling the pH value to 2.5-3.0, performing acid leaching at a temperature of 70-80 DEG C, and filtering to obtain leachate and lead slag; (2) replacing indium for the leachate by using zinc powder, and filtering to obtain indium slag; (3) performing rotational-flow electrodeposition arsenic removal and zinc removal on filtrate in sequence to obtain arsenic slag and zinc slag. The method disclosed by the invention can be used for purifying the acidic wastewater to reach a condition for recycling the acidic wastewater to a smelting acid manufacturing and purifying section, so that the treated acidic wastewater can be directly returned to the acid manufacturing and purifying section, and therefore, the gypsum slag is completely removed to truly achieve the purpose of zero emission. Meanwhile, the method disclosed by the invention can also be used for achieving the treatment of white soot and recycling the valuable metals, so that environmental protection and resource comprehensive utilization are achieved.
Description
Technical field
The invention belongs to smelting field of nonferrous metal, be specifically related to a kind of method reclaiming valuable metal containing arsenic smoke dust.
Background technology
White cigarette ash is flue gas dust collection gained cigarette ash in Metal smelting process, one of representational alkaline waste is had for industrial at present, wherein not only containing heavy metal valuable elements such as Pb, Bi, Zn, simultaneously containing harmful elements such as As, this waste processes not in time, not only can cause serious environmental pollution, also cause the waste of resource.Now conventional treatment process is directly by the process of direct for cigarette ash Returning smelting system; Aforesaid method not only reduces Flash Smelting Furnace processing power, worsens the working of a furnace, makes the objectionable constituent such as furnace charge As increase simultaneously.
Dirty acid is the spent acid washing flue gas generation in flue gas during smelting process of preparing sulfuric acid.In smeltery's fusion process, each heavy metal species and salt ion enter into flue gas and Dust in the form of a vapor, again through flue gas acid preparing, enter in the dirt acid of circulation.Therefore dirty acid contains the heavy metal ion such as Zn, Pb, As of a large amount of environmental pollution, dealing with improperly As in dirty acid especially to enter in air, water body and soil, absorbed by humans and animals by various approach such as respiratory tract, digestive tube and skins again, when these heavy metals humans and animals cylinder accumulation to a certain extent time, namely growing of humans and animals can directly be affected, physiology function, even causes the death of animal.Now conventional treatment process is all first neutralize dirty acid to neutral, precipitates by sulfuration method and lime method; Above-mentioned moderate water-cut stage can reach the object of the dirty acid of process, but generates the gypsum tailings that pile up like a mountain, takies a large amount of land resources, causes very serious pollution to environment.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method reclaiming valuable metal containing arsenic smoke dust is provided, thoroughly can eliminates the existence of gypsum tailings, also solve the disposal of white cigarette ash simultaneously, reclaim and have valency heavy metal.
The method reclaiming valuable metal containing arsenic smoke dust of the present invention, comprises the steps:
(1) by dirty acid and the mixing of white cigarette ash, control ph 2.5 ~ 3.0, carries out acidleach under temperature is 70 ~ 80 DEG C of conditions, filters to obtain leach liquor and lead skim;
(2) leach liquor zinc powder carries out displacement indium, filters to obtain indium slag;
(3) filtrate is successively through the dearsenification of eddy flow electrodeposition, dezincify, obtains arsenic slag and cadmia.
Described dirty acid is plumbous or the dirty acid of zinc abstraction, and white cigarette ash is Copper making cigarette ash.
The present invention is applicable to the cigarette ash comprehensively recovering valuable metal containing high arsenic, heavy metal, utilizes the dirty strongly-acid of acid and the alkalescence of white cigarette ash, carries out neutralizing, acidleach, and displacement is except indium, and eddy flow electrodeposition takes off As, de-Zn.This technique has purified dirty acid, reaches the condition that dirty acid is back to smelting acid making purification section, and the dirt acid processed can directly return relieving haperacidity purification section, thoroughly eliminates the existence of gypsum tailings, really reaches the object of zero release.Present invention addresses the disposal of white cigarette ash simultaneously, reclaimed and had valency heavy metal, reach environment protection and comprehensive utilization of resources.The advantages such as the inventive method has effect stability, efficient, simple to operate, technical process is short, and floor space is few.
Accompanying drawing explanation
Accompanying drawing 1 is present invention process schema.
Embodiment
For the ease of understanding the present invention, be explained by embodiment below.
Embodiment 1
The present embodiment dirty acid used is the dirty acid of plumbous smelting, and concrete composition is in table 1; White cigarette ash is Copper making cigarette ash, and concrete composition is in table 2.
(1) dirty acid and white cigarette ash mix by liquid-solid ratio 5: 1, and control ph 2.5 ~ 3.0, gets 500ml and carry out acidleach 2h under temperature is 70 DEG C of conditions.Filter to obtain leach liquor and lead skim.After testing, leach liquor is 380ml, and lead skim is 78.8g, and wherein the leaching yield of the leaching yield of As to be the leaching yield of 95.4%, Zn be 83.1%, Pb is only 2.34%, and the concrete data that leach are in table 3;
(2) leach liquor zinc powder carries out displacement indium, filters to obtain indium slag;
(3) filtrate is through the dearsenification of eddy flow electrodeposition, dezincify, and reclaim arsenic slag, cadmia, arsenic-removing rate is 99.2%, and dezinc degree is 58.7%, and concrete data are in table 4.After eddy flow electrodeposition, liquid can meet and is back to relieving haperacidity purification section.
Result shows: each heavy metal ion is reclaimed respectively by filtration, eddy flow electrodeposition, and lead recovery is 97.7%, and indium recovery is 76%, and the arsenic rate of recovery is 94.6%, and zinc recovery is 48.8%.
The dirty sour composition (g/L) of table 1
| Composition | H 2SO 4 | As | Cu | Zn | Pb | Fe | F | Cl | Cd |
| Dirty acid | 41.60 | 0.091 | Trace | 0.132 | 0.030 | 0.038 | 2.03 | 10.21 | 0.147 |
White cigarette ash major ingredient (quality %) smelted by table 2
| Composition | F | Cl | As | Bi | Zn | Pb | Cu | Cd | In |
| White cigarette ash | 0.036 | 0.150 | 13.78 | 1.05 | 3.04 | 48.46 | 0.361 | 1.17 | 0.035 |
Table 3 leach liquor and leached mud situation
| Element | F | Cl | As | Fe | Zn | Pb | Cu | Cd | In |
| Leach liquor, g/L | 1.85 | 9.67 | 28.47 | 2.78 | 8.80 | 0.04 | 0.029 | 3.10 | 0.0266 |
| Leached mud, quality % | 0.019 | 0.156 | 0.807 | 0.653 | 60.06 | 0.412 | 0.282 | 0.0084 | |
| Slag leaching yield % | 58.4 | 18.0 | 95.4 | 83.1 | 2.34 | 10.07 | 81.0 | 76 |
Table 4 is replaced except indium and eddy flow electrodeposition removal of impurities situation
Embodiment 2
The present embodiment dirty acid used is the dirty acid of zinc abstraction, and concrete composition is in table 5; White cigarette ash is Copper making cigarette ash, and concrete composition is in table 6.
(1) dirty acid and white cigarette ash mix by liquid-solid ratio 5: 1, and control ph 2.5 ~ 3.0, gets 500ml and carry out acidleach 2h under temperature is 80 DEG C of conditions.Filter to obtain leach liquor and lead skim.After testing, the leaching yield of the leaching yield of As to be the leaching yield of 95.7%, Zn be 82.8%, Pb is only 2.37%, and the concrete data that leach are in table 7;
(2) leach liquor zinc powder carries out displacement indium, filters to obtain indium slag;
(3) filtrate is through the dearsenification of eddy flow electrodeposition, dezincify, and reclaim arsenic slag, cadmia, arsenic-removing rate is 99.1%, and dezinc degree is 58.9, and concrete data are in table 8.After eddy flow electrodeposition, liquid can meet and is back to relieving haperacidity purification section.
Result shows: lead recovery is 97.63%, and indium recovery is 76%, and the arsenic rate of recovery is 94.8%, and zinc recovery is 48.8%.
The dirty sour composition (g/L) of table 5
| Composition | H 2SO 4 | As | Cu | Zn | Pb | Fe | F | Cl | Cd |
| Dirty acid | 31.23 | 0.238 | Trace | 0.329 | 0.0117 | 0.031 | 1.2 | 0.545 | 0.0267 |
White cigarette ash major ingredient (quality %) smelted by table 6
| Composition | F | Cl | As | Bi | Zn | Pb | Cu | Cd | In |
| White cigarette ash | 0.036 | 0.150 | 13.78 | 1.05 | 3.04 | 48.46 | 0.361 | 1.17 | 0.035 |
Table 7 leach liquor and leached mud situation
| Element | F | Cl | As | Fe | Zn | Pb | Cu | Cd | In |
| Leach liquor, g/L | 1.10 | 0.516 | 28.27 | 2.27 | 8.91 | 0.035 | 0.029 | 3.15 | 0.0266 |
| Leached mud, quality % | 0.011 | 0.008 | 0.801 | 0.656 | 59.86 | 0.412 | 0.282 | 0.0084 | |
| Slag leaching yield % | 58.1 | 18.1 | 95.7 | 82.8 | 2.37 | 10.07 | 80.5 | 76 |
Table 8 is replaced except indium and eddy flow electrodeposition removal of impurities situation
Claims (6)
1. reclaim a method for valuable metal containing arsenic smoke dust, comprise the steps:
(1) by dirty acid and the mixing of white cigarette ash, control ph 2.5 ~ 3.0, carries out acidleach under temperature is 70 ~ 80 DEG C of conditions, filters to obtain leach liquor and lead skim;
(2) leach liquor zinc powder carries out displacement indium, filters to obtain indium slag;
(3) filtrate is successively through the dearsenification of eddy flow electrodeposition, dezincify, obtains arsenic slag and cadmia.
2. the method reclaiming valuable metal containing arsenic smoke dust according to claim 1, is characterized in that dirty acid and white cigarette ash liquid-solid ratio 5: 1.
3. the method reclaiming valuable metal containing arsenic smoke dust according to claim 1 and 2, it is characterized in that described dirty acid is plumbous or the dirty acid of zinc abstraction, white cigarette ash is Copper making cigarette ash.
4. the method reclaiming valuable metal containing arsenic smoke dust according to claim 3, is characterized in that element mass content: Pb 48.46%, As 13.78%, Zn 3.04%, In 0.035% in white cigarette ash.
5. the method reclaiming valuable metal containing arsenic smoke dust according to claim 1 and 2, is characterized in that leaching time is 2h.
6. the method reclaiming valuable metal containing arsenic smoke dust according to claim 1 and 2, is characterized in that the electric effusion after the dezincify of eddy flow electrodeposition returns smelting acid making purification section.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
| CN105861844A (en) * | 2016-03-30 | 2016-08-17 | 湖南麓云达环境科技有限公司 | Comprehensive recycling method for non-ferrous metal metallurgy acidic wastewater and zinc-containing residues |
| CN107459166A (en) * | 2017-08-15 | 2017-12-12 | 昆明理工大学 | The curing of sour recycling and arsenic in a kind of waste acid |
| CN108642294A (en) * | 2018-05-11 | 2018-10-12 | 永兴众德环保科技有限公司 | A kind of multiple-effect evaporation waste acid dearsenicating technology |
| CN108754171A (en) * | 2018-07-02 | 2018-11-06 | 昆明冶金研究院 | The method of clean and effective recycling arsenic, copper, lead, antimony, silver in cupric smelting slag |
| CN109182764A (en) * | 2018-09-30 | 2019-01-11 | 昆明理工大学 | A kind of soda acid joint clean method of Copper making flue dust synthetical recovery |
| WO2019071642A1 (en) * | 2017-10-11 | 2019-04-18 | 北京科技大学 | Method for recovering lead from waste lead-acid battery lead paste in wet process |
| CN111378845A (en) * | 2020-04-17 | 2020-07-07 | 铜仁学院 | Method for recovering valuable metals from white smoke |
| CN113621818A (en) * | 2021-08-29 | 2021-11-09 | 中南大学 | Method for co-processing copper smelting waste acid and arsenic-containing smoke dust |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
| CN105861844A (en) * | 2016-03-30 | 2016-08-17 | 湖南麓云达环境科技有限公司 | Comprehensive recycling method for non-ferrous metal metallurgy acidic wastewater and zinc-containing residues |
| CN107459166A (en) * | 2017-08-15 | 2017-12-12 | 昆明理工大学 | The curing of sour recycling and arsenic in a kind of waste acid |
| WO2019071642A1 (en) * | 2017-10-11 | 2019-04-18 | 北京科技大学 | Method for recovering lead from waste lead-acid battery lead paste in wet process |
| US11502344B2 (en) | 2017-10-11 | 2022-11-15 | University Of Science And Technology Beijing | Hydrometallurgical method for recycling lead from spent lead-acid battery paste |
| CN108642294A (en) * | 2018-05-11 | 2018-10-12 | 永兴众德环保科技有限公司 | A kind of multiple-effect evaporation waste acid dearsenicating technology |
| CN108754171A (en) * | 2018-07-02 | 2018-11-06 | 昆明冶金研究院 | The method of clean and effective recycling arsenic, copper, lead, antimony, silver in cupric smelting slag |
| CN109182764A (en) * | 2018-09-30 | 2019-01-11 | 昆明理工大学 | A kind of soda acid joint clean method of Copper making flue dust synthetical recovery |
| CN111378845A (en) * | 2020-04-17 | 2020-07-07 | 铜仁学院 | Method for recovering valuable metals from white smoke |
| CN113621818A (en) * | 2021-08-29 | 2021-11-09 | 中南大学 | Method for co-processing copper smelting waste acid and arsenic-containing smoke dust |
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| CN104357668B (en) | 2016-08-17 |
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