CN101037725A - Method for treating arsenic pollution of copper smelt industry - Google Patents
Method for treating arsenic pollution of copper smelt industry Download PDFInfo
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- CN101037725A CN101037725A CNA2007100656538A CN200710065653A CN101037725A CN 101037725 A CN101037725 A CN 101037725A CN A2007100656538 A CNA2007100656538 A CN A2007100656538A CN 200710065653 A CN200710065653 A CN 200710065653A CN 101037725 A CN101037725 A CN 101037725A
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Abstract
The invention provides a method for controling arsenic pollution in the copper metallurgy industry, is characterized in that arsenic acid filtering case is added as vulcanized agent in sulphuric acid extract of copper metallurgy smoke to precipitate copper, copper slag and the solution containing copper are obtain by separation; the solution containing copper is contracted to 60-100 g/l of arsenical concentration and then cooled to the room temperature, heptahydrate zinc sulphate and crystal mother liquor are obtained after separation; sulfur dioxide is added to crystal mother liquor, thereby arsenic is dissolved out in the form of arsenic trioxide, arsenic trioxide and the solution after precipitating arsenic are obtained after separation, the solution after precipitating arsenic is back to smoke extract. The separature of the main component such as copper, arsenic, zinc and cadmium is performed in sulphuric acid extract of copper metallurgy smoke and arsenic acid filtering case with an objective for controling arsenic pollution economically and effectively, while provided with an advantage for further recycling valent metal synthetically.
Description
Technical field
The present invention relates to hydrometallurgy and environmental protection technical field, specifically administer the method for arsenic pollution of copper smelt industry.
Background technology
The Pollution abatement of copper smelt industry arsenic is subject to people's attention already.The dirty acid of the smelting smoke dust of output and sulfuric acid in the copper smelting process, contain metals such as copper, arsenic, zinc, cadmium, lead, bismuth, wherein arsenic content accounts for more than 50% of the total arsenic amount of copper smelting whole process, continuous progress along with the copper smelting technology, smelting process is taken off improving constantly of assorted ability, and be becoming tight the supply day of copper raw material, thereby the arsenic in the dirty acid of copper smelting smoke dust and sulfuric acid and the content of other volatile metal will be rising trend.
In the prior art, the processing of the dirty acid of copper smelting smoke dust and sulfuric acid is relatively independent.
To the processing of copper smelting smoke dust, adopt hydrometallurgical technology mostly, " the thick zinc sulfate of sulfuric acid leaching → electrodeposition decopper(ing) → condensing crystal → reduction sink arsenic → heavy arsenic liquid return leaching " technology wherein, the arsenic rate of recovery can reach 60%.
Processing to the dirty acid of sulfuric acid, " neutralization-molysite oxidation style " less expensive, waste water energy qualified discharge, but may redissolve owing to arsenic with slag in the output, there is secondary pollution, and store up and need take a large amount of land resources, if wherein the pollution of contained heavy metal is considered in the lump, the potential threat to environment is just bigger so; " sulfuration method " can obtain significant environmental benefit and social benefit, but has processing cost height and arsenic filter cake problem of outlet.
How economical, administer the arsenical pollution of the dirty acid of copper smelting smoke dust and sulfuric acid effectively, comprehensively reclaim wherein valuable metal, be still the difficult problem of copper smelt industry at present.
Summary of the invention
The purpose of this invention is to provide a kind of method of administering arsenic pollution of copper smelt industry, with the smelting smoke dust and the dirty sour arsenic filter cake combination treatment of output in the copper smelting process, realize separating of main component copper in copper smelting smoke dust sulphuric leachate and the dirty sour arsenic filter cake, arsenic, zinc, cadmium.
Technical scheme of the present invention is: in copper smelting smoke dust sulphuric leachate, add dirty sour arsenic filter cake as vulcanizing agent, make the copper precipitation, separate obtaining copper ashes and heavy copper liquid; It is 60～100g/L that the copper liquid that will sink is concentrated to arsenic concentration, is cooled to normal temperature again, obtains Zinc Sulphate Heptahydrate and crystalline mother solution through separating; In crystalline mother solution, feed sulfur dioxide gas, thus arsenic separate out with the white arsenic form, obtain liquid behind white arsenic and the heavy arsenic through separating again; Liquid returns the acidleach operation of sizing mixing behind the heavy arsenic.Whole process non-pollutant discharge is process for cleanly preparing.
The present invention is a technical foundation with " copper is smelted the method for high-arsenic dust sulphuric leachate separating copper arsenic zinc " patent of invention (application number CN200510048740.3), handle dirty sour arsenic filter cake that the dirty acid of sulfuric acid obtains as vulcanizing agent with prior art " sulfuration method ", make the copper precipitation in the copper smelting smoke dust sulphuric leachate, separate arsenic, zinc, cadmium then, reach the purpose of combined governance copper smelting smoke dust and dirty sour arsenic filter cake, create favorable conditions for further comprehensively recovering valuable metal simultaneously.
Key of the present invention is copper smelting smoke dust and dirty sour arsenic filter cake combination treatment, the treatment of wastes with processes of wastes against one another, economically feasible, the purpose that the arsenic contamination of realization copper smelting smoke dust and dirty sour arsenic filter cake is administered, significant to copper smelt industry environment protection treating and comprehensive utilization of resources.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment:
Certain copper smelting smoke dust main component is (%): Cu 4, As 8, Zn 10, Cd 2, Pb 25, Bi 2; Dirty sour arsenic filter cake main component is (%): Cu 1.7, As 26, S 18.
Implementation process is as follows:
1) sulfuric acid leaches: above-mentioned copper smelting smoke dust leaches with sulphuric acid soln, and liquid-solid ratio is 4: 1,50～80 ℃ of controlled temperature, and whole sour 5g/L, extraction time 2h filters and obtains leached mud and leach liquor.
2) the heavy copper of sulfuration: the leach liquor whipped state adds the sour arsenic filter cake of above-mentioned dirt down, 50～80 ℃ of controlled temperature, and the copper that sinks reaction stops to add dirty sour arsenic filter cake when being reacted to terminal point, filter and obtain copper ashes and heavy copper liquid.The determination methods of reaction end: the reaction soln that takes a morsel filters, and filtrate does not have blueness and is terminal point.
3) condensing crystal zinc sulfate: it is 60～100g/L that heavy copper liquid is concentrated to arsenic concentration, is cooled to normal temperature, filters and obtains Zinc Sulphate Heptahydrate (sulfur acid cadmium) and crystalline mother solution.
4) the heavy arsenic of reduction: crystalline mother solution normal temperature, whipped state feed sulfur dioxide gas down, reduce heavy arsenic reaction, stop logical sulfur dioxide gas when being reacted to terminal point, filter to obtain liquid behind white arsenic and the heavy arsenic, and liquid returns the acidleach operation of sizing mixing behind the heavy arsenic.The determination methods of reduction reaction terminal point: the reaction soln that takes a morsel filters, the concentration of filtrate analysis arsenic, and arsenic concentration is that 20g/L is terminal point.
Metal recovery rate is in the above-mentioned copper smelting smoke dust: arsenic＞60%, copper＞70%, zinc＞80%, cadmium＞80%, and lead, bismuth and remaining arsenic, copper, zinc, cadmium are stayed in the leached mud; Metal recovery rate is in the sour arsenic filter cake of above-mentioned dirt: arsenic＞95%, copper＞99%, sulfur recovery rate＞99%.
Claims (1)
1, a kind of method of administering arsenic pollution of copper smelt industry is characterized in that in copper smelting smoke dust sulphuric leachate, adds dirty sour arsenic filter cake as vulcanizing agent, makes the copper precipitation, separates obtaining copper ashes and heavy copper liquid; It is 60～100g/L that the copper liquid that will sink is concentrated to arsenic concentration, is cooled to normal temperature again, obtains Zinc Sulphate Heptahydrate and crystalline mother solution through separating; In crystalline mother solution, feed sulfur dioxide gas, thus arsenic separate out with the white arsenic form, obtain liquid behind white arsenic and the heavy arsenic through separating again; Liquid returns the flue dust leaching behind the heavy arsenic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100656538A CN101037725A (en) | 2007-02-06 | 2007-02-06 | Method for treating arsenic pollution of copper smelt industry |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100656538A CN101037725A (en) | 2007-02-06 | 2007-02-06 | Method for treating arsenic pollution of copper smelt industry |
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| CN101037725A true CN101037725A (en) | 2007-09-19 |
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| CNA2007100656538A Pending CN101037725A (en) | 2007-02-06 | 2007-02-06 | Method for treating arsenic pollution of copper smelt industry |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767822A (en) * | 2008-12-31 | 2010-07-07 | 江西铜业集团公司 | Method for recovering arsenic from scrap material containing arsenic and copper produced in process of copper smelting |
| CN101857297A (en) * | 2010-06-01 | 2010-10-13 | 河南豫光金铅股份有限公司 | Method for processing waste acid water discharged by system for preparing sulfuric acid from lead or zinc smelting flue gas |
| CN102120636A (en) * | 2011-01-21 | 2011-07-13 | 哈尔滨工业大学深圳研究生院 | Method and device for removing heavy metals in industrial wastewater |
| CN101619398B (en) * | 2009-07-27 | 2011-07-27 | 昭通天元实业有限责任公司 | Method for extracting arsenic from pyrite cinder |
| CN102351360A (en) * | 2011-07-04 | 2012-02-15 | 锡矿山闪星锑业有限责任公司 | Method for comprehensive recovery of arsenic-containing alkaline liquid and waste gas of sulfur dioxide |
| CN102851497A (en) * | 2012-09-21 | 2013-01-02 | 北京矿冶研究总院 | Method for treating arsenic-containing material |
| CN103014355A (en) * | 2012-12-13 | 2013-04-03 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN105536475A (en) * | 2015-12-30 | 2016-05-04 | 山东恒邦冶炼股份有限公司 | Arsenic recovery process for sulfur trioxide-containing smelting flue gas |
| CN105543480A (en) * | 2015-12-28 | 2016-05-04 | 中南大学 | Method for separation and enrichment of copper and arsenic in copper smelting acidic wastewater |
| CN105603466A (en) * | 2015-12-28 | 2016-05-25 | 中南大学 | Method for efficiently separating and recycling copper and arsenic in copper electrolyte |
| CN105776703A (en) * | 2016-04-08 | 2016-07-20 | 南通三圣石墨设备科技股份有限公司 | Method for processing smelting waste acid |
| CN106521167A (en) * | 2016-10-11 | 2017-03-22 | 昆明理工大学 | Comprehensive treatment method for high-arsenic lead zinc flue dust ash |
| CN108034830A (en) * | 2017-12-24 | 2018-05-15 | 江西理工大学 | A kind of method of valuable metal in Recovering Copper smelting ash |
| CN110116991A (en) * | 2019-05-21 | 2019-08-13 | 长沙有色冶金设计研究院有限公司 | A kind of recovery process of metallurgical off-gas acid-making purification waste acid |
| CN110983059A (en) * | 2019-12-09 | 2020-04-10 | 黑龙江紫金铜业有限公司 | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake |
| CN110983060A (en) * | 2019-12-09 | 2020-04-10 | 黑龙江紫金铜业有限公司 | Method for resource utilization of arsenic filter cake and white smoke |
| CN111334665A (en) * | 2020-03-12 | 2020-06-26 | 昆明理工大学 | Method for separating indium, copper, arsenic and zinc from multi-metal sulfuric acid solution |
| CN111349790A (en) * | 2020-03-30 | 2020-06-30 | 北京矿冶科技集团有限公司 | Method for reducing arsenic content in copper smelting soot leaching slag |
| CN115369252A (en) * | 2022-08-02 | 2022-11-22 | 云南铜业股份有限公司西南铜业分公司 | Treatment method of copper smelting white smoke dust |
| CN116463514A (en) * | 2023-04-19 | 2023-07-21 | 昆明瀚创科技有限公司 | Treatment method of arsenic-containing smoke leaching residues in copper smelting |
-
2007
- 2007-02-06 CN CNA2007100656538A patent/CN101037725A/en active Pending
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767822A (en) * | 2008-12-31 | 2010-07-07 | 江西铜业集团公司 | Method for recovering arsenic from scrap material containing arsenic and copper produced in process of copper smelting |
| CN101619398B (en) * | 2009-07-27 | 2011-07-27 | 昭通天元实业有限责任公司 | Method for extracting arsenic from pyrite cinder |
| CN101857297A (en) * | 2010-06-01 | 2010-10-13 | 河南豫光金铅股份有限公司 | Method for processing waste acid water discharged by system for preparing sulfuric acid from lead or zinc smelting flue gas |
| CN101857297B (en) * | 2010-06-01 | 2011-12-14 | 河南豫光金铅股份有限公司 | Method for processing waste acid water discharged by system for preparing sulfuric acid from lead or zinc smelting flue gas |
| CN102120636A (en) * | 2011-01-21 | 2011-07-13 | 哈尔滨工业大学深圳研究生院 | Method and device for removing heavy metals in industrial wastewater |
| CN102120636B (en) * | 2011-01-21 | 2012-07-04 | 哈尔滨工业大学深圳研究生院 | Method and device for removing heavy metals in industrial wastewater |
| CN102351360A (en) * | 2011-07-04 | 2012-02-15 | 锡矿山闪星锑业有限责任公司 | Method for comprehensive recovery of arsenic-containing alkaline liquid and waste gas of sulfur dioxide |
| CN102851497B (en) * | 2012-09-21 | 2014-07-23 | 北京矿冶研究总院 | Method for treating arsenic-containing material |
| CN102851497A (en) * | 2012-09-21 | 2013-01-02 | 北京矿冶研究总院 | Method for treating arsenic-containing material |
| CN103014355A (en) * | 2012-12-13 | 2013-04-03 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN103014355B (en) * | 2012-12-13 | 2014-12-24 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN105543480A (en) * | 2015-12-28 | 2016-05-04 | 中南大学 | Method for separation and enrichment of copper and arsenic in copper smelting acidic wastewater |
| CN105603466A (en) * | 2015-12-28 | 2016-05-25 | 中南大学 | Method for efficiently separating and recycling copper and arsenic in copper electrolyte |
| CN105603466B (en) * | 2015-12-28 | 2018-03-30 | 中南大学 | A kind of method for efficiently separating copper arsenic in recovery copper electrolyte |
| CN105543480B (en) * | 2015-12-28 | 2017-08-25 | 中南大学 | A kind of method of copper arsenic separation and concentration in Copper making waste acid |
| CN105536475A (en) * | 2015-12-30 | 2016-05-04 | 山东恒邦冶炼股份有限公司 | Arsenic recovery process for sulfur trioxide-containing smelting flue gas |
| CN105536475B (en) * | 2015-12-30 | 2018-01-12 | 山东恒邦冶炼股份有限公司 | A kind of receipts arsenic technique of the flue gas during smelting containing sulfur trioxide |
| CN105776703A (en) * | 2016-04-08 | 2016-07-20 | 南通三圣石墨设备科技股份有限公司 | Method for processing smelting waste acid |
| CN106521167B (en) * | 2016-10-11 | 2018-10-02 | 昆明理工大学 | A kind of integrated conduct method of high concn. arsenic and lead Zn dust ash |
| CN106521167A (en) * | 2016-10-11 | 2017-03-22 | 昆明理工大学 | Comprehensive treatment method for high-arsenic lead zinc flue dust ash |
| CN108034830A (en) * | 2017-12-24 | 2018-05-15 | 江西理工大学 | A kind of method of valuable metal in Recovering Copper smelting ash |
| CN110116991B (en) * | 2019-05-21 | 2020-12-22 | 长沙有色冶金设计研究院有限公司 | Recovery process for purifying waste acid by making acid from smelting flue gas |
| CN110116991A (en) * | 2019-05-21 | 2019-08-13 | 长沙有色冶金设计研究院有限公司 | A kind of recovery process of metallurgical off-gas acid-making purification waste acid |
| CN110983059B (en) * | 2019-12-09 | 2021-07-06 | 黑龙江紫金铜业有限公司 | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake |
| CN110983060A (en) * | 2019-12-09 | 2020-04-10 | 黑龙江紫金铜业有限公司 | Method for resource utilization of arsenic filter cake and white smoke |
| CN110983059A (en) * | 2019-12-09 | 2020-04-10 | 黑龙江紫金铜业有限公司 | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake |
| CN110983060B (en) * | 2019-12-09 | 2021-07-06 | 黑龙江紫金铜业有限公司 | Method for resource utilization of arsenic filter cake and white smoke |
| CN111334665A (en) * | 2020-03-12 | 2020-06-26 | 昆明理工大学 | Method for separating indium, copper, arsenic and zinc from multi-metal sulfuric acid solution |
| CN111349790A (en) * | 2020-03-30 | 2020-06-30 | 北京矿冶科技集团有限公司 | Method for reducing arsenic content in copper smelting soot leaching slag |
| CN115369252A (en) * | 2022-08-02 | 2022-11-22 | 云南铜业股份有限公司西南铜业分公司 | Treatment method of copper smelting white smoke dust |
| CN116463514A (en) * | 2023-04-19 | 2023-07-21 | 昆明瀚创科技有限公司 | Treatment method of arsenic-containing smoke leaching residues in copper smelting |
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