CN102994765B - Method for treating waste copper slag - Google Patents
Method for treating waste copper slag Download PDFInfo
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- CN102994765B CN102994765B CN201210520356.9A CN201210520356A CN102994765B CN 102994765 B CN102994765 B CN 102994765B CN 201210520356 A CN201210520356 A CN 201210520356A CN 102994765 B CN102994765 B CN 102994765B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention provides a method for treating waste copper slag. The method is characterized by respectively obtaining copper concentrate, ferrum concentrate and waste materials containing lead and zinc smoke and capable of being used for air-entrapping bricks according to the process route of floatation, reduction-oxidation roasting of a rotary kiln and magnetic separation in sequence; according to the process scheme, the method comprises the following steps: a. floating 90% of 200-mesh waste copper slag with fine grinding size of smaller than 74mu m to obtain the copper concentrate and primary tailings; b. conducting reduction-oxidation roasting to the primary tailings in the rotary kiln, recovering lead and zinc through smoke, conducting magnetic separation on the roasted product to obtain the ferrum concentrate and the final tailings; and c. taking the final tailings as raw materials of aerated concrete products to produce air-entrapping bricks. The method has the advantages of being clean, environment-friendly and zero-emission in waste copper slag treatment process, not only realizing the effective recovery of resources, and reducing environmental pollution, but also obtaining good economic benefits.
Description
Technical field:
The present invention relates to solid waste renewable resource comprehensive utilization technique field, particularly relate to a kind for the treatment of process that reclaims copper, iron, lead, zinc from waste copper slag.
Background technology:
In the prior art, along with economic, social development, copper output and copper consumption constantly increase, and meanwhile, producing in the process of smelting various copper products, are also discharging a large amount of mine tailings and waste copper slag; The main component of its waste copper slag generally contains Cu, Fe, SiO
2, S, also have a certain amount of Pb, Zn etc.; The existence of a large amount of waste copper slags, not only takies many soils, is also unfavorable for production and administration; And the flushing of rainwater also can make, in the heavy metal infiltration soil and groundwater in slag, to cause ecosystem environment to pollute.On the other hand, copper smelts that in the waste copper slag producing, Cu content is approximately more than 0.5%, and iron level reaches 40%, in the situation that copper mine and iron ore deposit reduce increasingly, how to realize comprehensive utilization and the Sustainable development of resource, become the task of top priority of society and enterprise development.At present, increasing Chinese scholars begins one's study the valuable metal recovery in iron melting waste slag, but effect is all not too obvious, especially inadequate to reclaiming to greatest extent the fundamental research of the valuable metals such as copper, iron, lead, zinc in copper ashes, and the method adopting is confined to adopt Physical ore dressing to realize the recovery of one or both metals mostly, and organic efficiency is lower; Or adopt wet-leaching technique, but technical process is long, cost is high and the recycling of unrealized plumbous zinc.Japanese, Chilean external was once studied copper content and adopted directly and leach higher than 4% blister copper converter slag, and---technique of leaching recycles direct flotation---oxidation or sulfurization roasting---, but the research that copper content is less than the copper smelting slag of 1% left and right be there is not yet to report.
Summary of the invention:
The object of the invention is to extract and utilize the renewable resource of waste copper slag, eliminate and reduce the negative impact that brings to ecosystem environment of waste copper slag, a kind of recyclable copper ore concentrates, iron ore concentrate being provided, being rich in Pb-Zn dust and can be used for the treatment process of the waste copper slag of the leftover materials that do aerated bricks.
The present invention solves the scheme that its technical problem adopts: a kind for the treatment of process of waste copper slag is provided, and waste copper slag method for floating is: waste copper slag enters ball mill through straight line shaker classification screen underflow; Ball mill and duplex-spiral classifier form closed circuit grinding classification technique, make waste copper slag granularity be less than 74 μ m(200 orders) account for more than 90%; After mill, the slag of release mesh adopts the floatation process of " roughly selecting-tri-selected-tri-scans " to produce copper ore concentrates; Adopt wet magnetic separation to separate and obtain iron ore concentrate and ultimate tailings; Aerated bricks making method be ultimate tailings with addition of quartz sand, lime stone-gypsum, cement, through preparing burden, stir, be poured in mould, form aerated bricks base substrate; It is characterized in that: by the operational path of " flotation → rotary kiln reduction-oxidation roasting → magnetic separation ", can obtain respectively copper ore concentrates, iron ore concentrate, be rich in Pb-Zn dust and can be used for doing the leftover materials of aerated bricks; Rotary kiln reduction-oxidation roasting method is: elementary tailings is with addition of lime, coal, in rotary kiln, control reaction atmosphere in rotary kiln, its volatilization is entered in flue gas zinc reduction in elementary mine tailing in advance, flue gas reclaims zinc with sack cleaner after cooling with the form of oxide compound; Lead also enters in flue gas with halid form volatilization; The flue dust reclaiming is rich in plumbous zinc and can be used as the raw material of lead-zinc smelting; After the product calcining of later stage oxidizing roasting is cooling, be finely ground to granularity and be less than 74 μ m(200 orders) account for more than 90%; Waste copper slag copper content 0.4-1%, iron-holder 20-50%, leaded, zinc amount 2-10%; In rotary kiln reduction-oxidation roasting method, prepare burden: elementary tailings 65-85%; Coal 5-10%; Lime 10-25%; 950～1050 ℃ of rotary kiln reduction temperatures in rotary kiln reduction-oxidation roasting method, 1050～1200 ℃ of oxidizing roasting temperature; In rotary kiln reduction-oxidation roasting method, kiln temperature control section is divided into: dry heat section (normal temperature～950 ℃)---reduction section (950～1050 ℃)---oxidation panel (1050～1200 ℃)---slow cooling section (1050～650 ℃); Material total residence time 2-4 hour in rotary kiln in rotary kiln reduction-oxidation roasting method, the each period of residence time: dry heat section 30min～60min, reduction section 30min～60min, oxidation panel 45min～90min, slow cooling section 15min～30min; Wet magnetic separation control parameter: weak magnetic magnetic induction 120～200mT; Strong magnetic magnetic induction 1500～2300mT; Copper ore concentrates adopts and concentrates, filters two stage dewatering technologies, dehydration rate 10%-15%.
The invention has the beneficial effects as follows: owing to having fully utilized the renewable resource of waste copper slag, eliminate and reduced the negative impact that waste copper slag brings to ecosystem environment, reclaim copper ore concentrates, iron ore concentrate, be rich in Pb-Zn dust and can be used for doing the leftover materials of aerated bricks, both realized the effective recycling of resource, also reduce environmental pollution, and obtained good social and economic benefits.
Accompanying drawing explanation:
Fig. 1 is the process flow sheet of the treatment process of a kind of waste copper slag of patent working example of the present invention.
Concrete implementation content:
Embodiment 1: concrete implementation content is by the typical waste copper slag sample of certain copper smelting plant, 10kg(TFe=39.4%, Cu=0.62%, Zn=2.69% altogether, Pb=0.63%) process by technical process of the present invention, its treating processes is: (1) fine grinding waste copper slag to granularity is less than 74 μ m(200 orders) account for more than 90%, adopt flotation to produce copper ore concentrates.Concrete technology: roughly select, three sections selected, three sections scan and produce final copper ore concentrates (cupric 15%) and elementary mine tailing; (2) elementary tailings, with addition of 15% lime, 10% coal, fully mixes, and simulates the processing condition of rotary kiln in tube type resistance furnace, in the time of 1000 ℃, is incubated 1 hour, in the time of 1100 ℃, is incubated 1 hour; First reduce rear oxidation roasting.Reclaim flue dust with sack cleaner, and the product of cooled oxidizing roasting is finely ground to granularity is less than 74 μ m(200 orders) account for more than 90%, adopt wet magnetic separation to separate and obtain iron ore concentrate (iron content 60%) and ultimate tailings; (3) ultimate tailings is with addition of quartz sand, lime stone-gypsum, cement, through batching, stirring, castable aerated bricks.Typical waste copper slag sample (10kg altogether) by operational path of the present invention to certain copper smelting plant is processed, obtain respectively the copper ore concentrates 0.3kg of cupric 15%, the iron ore concentrate 5.8kg of iron content 60%, be rich in the leaded zinc 30% of Pb-Zn dust 0.5kg() and the doping material 7.1kg of aerated bricks, realize the comprehensive utilization of waste copper slag.
Embodiment 2, concrete implementation content are by the typical waste copper slag sample of certain copper smelting plant, 10kg(TFe=39.4%, Cu=0.62%, Zn=2.69% altogether, Pb=0.63%) process by technical process of the present invention, its treating processes is: (1) fine grinding waste copper slag to granularity is less than 74 μ m(200 orders) account for more than 95%, adopt flotation to produce copper ore concentrates, concrete technology: roughly select, three sections selected, three sections scan and produce final copper ore concentrates (cupric 12%) and elementary mine tailing.(2) elementary tailings, with addition of 20% lime, 8% coal, fully mixes, and simulates the processing condition of rotary kiln in tube type resistance furnace, in the time of 1050 ℃, is incubated 40 minutes, in the time of 1150 ℃, is incubated 50 minutes; First reduce rear oxidation roasting; Reclaim flue dust with sack cleaner; And the product of cooled oxidizing roasting be finely ground to granularity be less than 74 μ m(200 orders) account for more than 95%; Adopt wet magnetic separation to separate and obtain iron ore concentrate (iron content 58%) and ultimate tailings.(3) ultimate tailings is with addition of quartz sand, lime stone-gypsum, cement, through batching, stirring, castable.Typical waste copper slag sample (10kg altogether) by operational path of the present invention to certain copper smelting plant carries out comprehensive treating process, obtain respectively the copper ore concentrates 0.5kg of cupric 12%, the iron ore concentrate 6.8kg of iron content 58%, be rich in the leaded zinc 30% of Pb-Zn dust 0.5kg() and aerated bricks doping material 8.1kg, realize the comprehensive utilization of waste copper slag.
Embodiment 3, concrete implementation content are by the typical waste copper slag sample of certain copper smelting plant, 1500kg(TFe=39.4%, Cu=0.62%, Zn=2.69% altogether, Pb=0.63%) process by technique of the present invention, its treating processes is: (1) fine grinding waste copper slag to granularity is less than 74 μ m(200 orders) account for more than 90%, adopt flotation to produce copper ore concentrates.Concrete technology: roughly select, three sections selected, three sections scan and produce final copper ore concentrates (cupric 13%) and elementary mine tailing.(2) elementary tailings, with addition of 12% lime, 6% coal, fully mixes, and in rotary kiln, 1020 ℃ of insulations 5 minutes, 1080 ℃ were incubated 50 minutes; First reduce rear oxidation roasting.Reclaim flue dust with sack cleaner, and the product of cooled oxidizing roasting is finely ground to granularity is less than 74 μ m(200 orders) account for more than 90%, adopt wet magnetic separation to separate and obtain iron ore concentrate (iron content 62%) and ultimate tailings.(3) ultimate tailings is with addition of quartz sand, lime stone-gypsum, cement, through batching, stirring, castable.Typical waste copper slag sample (1500kg altogether) by operational path of the present invention to certain copper smelting plant cleans processing, obtain respectively the copper ore concentrates 48kg of cupric 13%, the iron ore concentrate 870kg of iron content 60%, be rich in the leaded zinc 30% of Pb-Zn dust 75kg() and aerated bricks doping material 627kg, realize the comprehensive utilization of waste copper slag.
Claims (1)
1. a treatment process for waste copper slag, waste copper slag method for floating is: waste copper slag enters ball mill through straight line shaker classification screen underflow; Ball mill and duplex-spiral classifier form closed circuit grinding classification technique, make waste copper slag granularity be less than 74 μ m(200 orders) account for more than 90%, after mill, the slag of release mesh adopts the floatation process of " roughly selecting-tri-selected-tri-scans " to produce copper ore concentrates; Adopt wet magnetic separation to separate and obtain iron ore concentrate and ultimate tailings; Aerated bricks making method be ultimate tailings with addition of quartz sand, lime stone-gypsum, cement, through preparing burden, stir, be poured in mould, form aerated bricks base substrate; It is characterized in that: by the operational path of " flotation → rotary kiln reduction-oxidation roasting → magnetic separation ", can obtain respectively copper ore concentrates, iron ore concentrate, be rich in Pb-Zn dust and can be used for doing the leftover materials of aerated bricks; Rotary kiln reduction-oxidation roasting method is: elementary tailings is with addition of lime, coal, in rotary kiln, control reaction atmosphere in rotary kiln, its volatilization is entered in flue gas zinc reduction in elementary mine tailing in advance, flue gas reclaims zinc with sack cleaner after cooling with the form of oxide compound; Lead also enters in flue gas with halid form volatilization; The flue dust reclaiming is rich in plumbous zinc and can be used as the raw material of lead-zinc smelting; After the product calcining of later stage oxidizing roasting is cooling, be finely ground to granularity and be less than 74 μ m(200 orders) account for more than 90%; Waste copper slag copper content 0.4-1%, iron-holder 20-50%, leaded, zinc amount 2-10%; In rotary kiln reduction-oxidation roasting method, prepare burden: elementary tailings 65-85%; Coal 5-10%; Lime 10-25%; 950～1050 ℃ of rotary kiln reduction temperatures in rotary kiln reduction-oxidation roasting method, 1050～1200 ℃ of oxidizing roasting temperature; In rotary kiln reduction-oxidation roasting method, kiln temperature control section is divided into: dry heat section (normal temperature～950 ℃)---reduction section (950～1050 ℃)---oxidation panel (1050～1200 ℃)---slow cooling section (1050～650 ℃); Material total residence time 2-4 hour in rotary kiln in rotary kiln reduction-oxidation roasting method, the each period of residence time: dry heat section 30min～60min, reduction section 30min～60min, oxidation panel 45min～90min, slow cooling section 15min～30min; Wet magnetic separation control parameter: weak magnetic magnetic induction 120～200mT; Strong magnetic magnetic induction 1500～2300mT; Copper ore concentrates adopts and concentrates, filters two stage dewatering technologies, dehydration rate 10%-15%.
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| CN103436707B (en) * | 2013-08-19 | 2016-06-22 | 昆明理工大学 | A kind of reclaim the method for ferrum, indium, stannum in Zinc volatilization kiln kiln slag |
| CN105177300A (en) * | 2014-06-04 | 2015-12-23 | 北京中冶设备研究设计总院有限公司 | Method for processing water-quenched copper slag and recycling iron, lead and zinc with rotary kiln |
| CN105271958B (en) * | 2014-06-04 | 2018-09-21 | 北京中冶设备研究设计总院有限公司 | A method of producing air entrained concrete with selecting copper to carry the water quenching copper tailings after iron |
| CN104141049B (en) * | 2014-08-04 | 2016-10-12 | 云南天地行节能科技有限公司 | The integrated treatment of a kind of zinc slag utilizes technique |
| CN104294032B (en) * | 2014-09-30 | 2016-09-07 | 池煊庆 | The comprehensive recovering process of oxidation tin ore gravity tailings |
| CN104846214B (en) * | 2015-04-21 | 2017-05-10 | 云南驰宏锌锗股份有限公司 | Method for processing heavy metal-containing gypsum residue by oxygen-rich top-blown lead smelting furnace |
| CN104975123A (en) * | 2015-07-06 | 2015-10-14 | 中冶建筑研究总院有限公司 | Method for preparing copper-containing cast iron and slag cotton from molten copper slag |
| CN106916958B (en) * | 2017-03-15 | 2018-11-09 | 中南大学 | A kind of method of copper smelting slag direct-reduction recycling iron |
| CN108034819B (en) * | 2017-09-11 | 2019-07-30 | 江西新金叶实业有限公司 | A method of copper is extracted using oxygen-enriched smelting method |
| CN108048647A (en) * | 2017-11-07 | 2018-05-18 | 江苏省冶金设计院有限公司 | A kind of processing method of copper ashes |
| CN107904409A (en) * | 2017-11-23 | 2018-04-13 | 江苏省冶金设计院有限公司 | The method for handling copper ashes |
| CN111921700A (en) * | 2020-07-13 | 2020-11-13 | 黑龙江科技大学 | Method for comprehensively recovering multiple metals in copper smelting slag |
| CN112226624A (en) * | 2020-10-22 | 2021-01-15 | 矿冶科技集团有限公司 | Method for co-processing copper slag and zinc slag |
| CN115159998A (en) * | 2022-07-05 | 2022-10-11 | 武汉科技大学 | Refractory silica brick and method for preparing refractory silica brick by using copper slag |
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Inventor after: Zhang Jinliang Inventor after: Guo Mingwei Inventor after: Zhou Chunfang Inventor after: Guo Hua Inventor after: Zhao Weijie Inventor after: Huang Chao Inventor after: Zhang Fuxin Inventor before: Zhang Jinliang Inventor before: Guo Mingwei Inventor before: Zhou Chunfang Inventor before: Guo Hua Inventor before: Zhao Weijie Inventor before: Huang Chao Inventor before: Zhang Fuxin |