CN101812598B - Method for simultaneously smelting zinc dipping slag and zinc kiln slag by using blast furnace - Google Patents
Method for simultaneously smelting zinc dipping slag and zinc kiln slag by using blast furnace Download PDFInfo
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- CN101812598B CN101812598B CN2010101319730A CN201010131973A CN101812598B CN 101812598 B CN101812598 B CN 101812598B CN 2010101319730 A CN2010101319730 A CN 2010101319730A CN 201010131973 A CN201010131973 A CN 201010131973A CN 101812598 B CN101812598 B CN 101812598B
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Abstract
The invention relates to a method for simultaneously smelting zinc dipping slag and zinc kiln slag by using a blast furnace, which belongs to the technical field of metal smelting. The method comprises the following steps: a, taking a certain amount of zinc dipping slag, adding 10 to 20 percent of water into the zinc dipping slag to form a zinc dipping slag briquette, and naturally drying the zinc dipping slag briquette for 10 to 16 hours at a ventilated place for later use; b, taking 46 to 60 percent of zinc kiln slag of which over 75 percent meets the initial granularity requirement of 10 meshes, adding 22 to 34 percent of zinc dipping slag briquette, 15 percent of coke and 2 to 5 percent of silica into the zinc kiln slag, mixing the four materials and smelting the mixture; c, smelting the mixture in the blast furnace, wherein the smelting temperature is between 600 and 1,350 DEG C, the smelting period is 40 to 80 minutes and the tuyere ratio distribution range of the blast furnace is 4.5 to 6.1 percent; and d, obtaining a copper matte phase, a soot phase and a slag phase after the mixture is smelted in the blast furnace. Reclaimed copper, gold and silver phases in the copper matte phase are directly used as raw materials for smelting copper; reclaimed zinc and lead valuable elements in the soot phase are directly used as raw materials for smelting zinc and lead; and the slag phase is directly used as a raw material for producing cement. The method has the advantages of simultaneously obtaining the copper matte, the slag phase and the soot serving as primary products through one process, realizing efficient separation and zero emission of the valuable elements, along with environment protection.
Description
Technical field:
The present invention relates to a kind of method of extracting valuable metal element in zinc kiln slag and the zinc leaching residue, adopt specifically blast furnace to zinc kiln slag and zinc leaching residue carry out jointly melting obtain matte mutually, flue dust mutually and slag method mutually.Belong to the Metal smelting technical field.
Background technology:
Zinc leaching residue is a kind of solid castaway slag that produces in the zinc hydrometallurgy process, contains valuable metal elements such as zinc, lead, copper, iron, gallium, germanium, indium and silver, has great comprehensive utilization value.Zinc kiln slag is the coke powder of zinc leaching residue with addition of 40～50% of zinc hydrometallurgy, extracts the castaway slag behind the metals such as zinc, lead in rotary kiln under the high temperature.Can be detained valuable metals such as many iron, zinc, copper, lead, silver, gold generally speaking, be the comprehensive recovery raw material that marketable value is arranged very much.Blast furnace is a kind of metallurgical technology equipment of half autothermal oxidation melting, has reduced investment, easy to operate, floor space is little and melting condition is good characteristics.Zinc leaching residue mostly adopts the rotary kiln fuming process to handle, to reclaim the part valuable element in the zinc leaching residue, and most rare precious metal enters in the zinc kiln slag, forms alloy or silicate compound and is difficult to handle, and causes rare precious metal resource heavy losses and environmental pollution.Known document 1 (Huang Zhucheng, Yang Yongbin, Cai Jiangsong etc. the enrichment behavior of zinc leaching residue comprehensive utilization novel process and gallium. the journal .2002 of Zhongnan Polytechnic Univ, 33 (2): 132-136) adopt the experimentize research of chamber of reduction roasting method, be under reductive atmosphere, reclaimed metallic elements such as gallium, iron, zinc.Recycle for valuable element in the zinc kiln slag, known document 2 (Zhou Hongwu, Xu Ziping. smelting bath smelting process reclaims silver [J] from zinc kiln slag. non-ferrous metal (smelting part), 1991 (6): 18～20) adopt smelting bath smelting process to reclaim valuable element in the zinc kiln slag, also only proceeding to the lab scale experiment and the dissipated metal rate of recovery is about 40%, and has subsequent disposal and sulfur dioxide pollution environmental problem.Known document 3 (Li Changfu. the experimental study of all mouthful of kiln slag smelting technology. mining and metallurgy .2002,11 (3): 56-59) adopt the sulfurized technology to handle zinc kiln slag with pyrite, can reclaim valuable element in the zinc kiln slag, but the sulfurous gas that this technology has only carried out producing in breadboard research and the technology can worsen processing environment.Known document 4 (Liu Zhihongs, Wen Jian, Li Yuhu, Deng. the research [J] of all mouthful of kiln slag comprehensively recovering valuable metal of fusion chloridizing volatilization art breading. non-ferrous metal (smelting part), 2005 (3): 14-15) adopt the fusion chlorination process in flue dust, to reclaim valuable element in the zinc kiln slag, the evaporation rate of zinc and copper is on the low side, and the volatilization index of zinc is undesirable, has also that fume amount is big, dust polluting environment and villaumite be to treatment facility corrosive problem; Therefore, the short and good in economic efficiency processing zinc kiln slag of valuable element high efficiency separation, environmental friendliness, technical process and the technology of zinc leaching residue just have practical significance.
Summary of the invention:
The objective of the invention is to overcome the deficiency of prior art, and a kind of method with blast furnace while melting zinc kiln slag and zinc leaching residue is provided.
The present invention adopts blast furnace, and unmanageable solid castaway slag zinc kiln slag and zinc leaching residue are carried out the while melting, reclaims the valuable metal element.Extraction principle of the present invention is as follows:
Matte smelting reaction: (Cu
2O)+[FeS]=[Cu
2S]+(FeO)
(MeO)+[FeS]＝[MeS]+(FeO)
The solubilizing reaction of precious metal:
[Cu
2S]+[FeS]+Ag
2S→[Cu
2S·FeS·Ag
2S]
[Cu
2S]+[FeS]+Ag→[Cu
2S·FeS·Ag]
[Cu
2S]+[FeS]+Au→[Cu
2S·FeS·Au]
The slag making reaction:
3Fe
3O
4+FeS+5SiO
2＝5(2FeO·SiO
2)+SO
2
FeO+CaO+2SiO
2＝(FeO·CaO·2SiO
2)
Method of the present invention comprises the briquetting of zinc leaching residue, the batching of zinc kiln slag, coke, quartz and zinc leaching residue nodulizing, the blast furnace smelting of mixture, and the processing of smelted product; Material is mass percent with ratio in the method, and concrete steps are as follows:
A. get a certain amount of zinc leaching residue and 10～20% water mix naturally, the initial particle size of zinc leaching residue requires-200 orders to account for more than 70%, carries out briquetting then in the disk briquetting machine, obtains the zinc leaching residue nodulizing, and is standby behind ventilation seasoning 10-16h;
B. get zinc kiln slag 46～60%, initial particle size requires+10 orders to account for more than 75%; Allocate zinc leaching residue nodulizing 22～34%, coke 15%, silica 2～5% into; Enter melting in the blast furnace after four kinds of mixing of materials;
C. mixture carries out the processing condition of blast furnace smelting and is: the blast furnace smelting temperature is 600～1300 ℃, and melting cycle is 40～80min, and the air port of blast furnace is 4.5～6.1%% than distribution scope;
D. zinc kiln slag and zinc leaching residue behind blast furnace smelting, obtain matte mutually, flue dust mutually with slag mutually; The enrichment of matte phase copper, gold and silver-colored valuable element, adopt the copper metallurgy principle process to reclaim copper, Jin Heyin, directly as the raw material of copper metallurgy; Flue dust is rich in zinc and lead element mutually, adopts the mode of bag collection to reclaim the zinc in the flue dust, plumbous valuable element, direct raw material as zinc metallurgy, lead; Slag contains iron, silicon and calcium constituent mutually, directly as the raw material of producing cement.Characteristics of the present invention:
1, the employing blast furnace reclaims the valuable metal element in zinc leaching residue and the zinc kiln slag simultaneously, has both solved environmental issue, meets the Development patterns of recycling economy again, and rate of recovery height.Copper, gold and silver raising recovery rate are all more than 95%, and lead and zinc evaporation rate are all more than 95%.
2, melting system adopts oxidizing atmosphere and material energy self-heating.Because blast furnace blasts a large amount of air, keeps whole blast furnace material system and belongs to oxidizing atmosphere, has strengthened the melting condition of blast furnace; Zinc kiln slag itself contains part, can make the carbon of fuel.
3, good, the environmental friendliness of product separating effect, technical process is short and equipment is simple and practical.Copper, gold and silver and part ferro element enter matte mutually, as the raw material of copper metallurgy; Part iron, silicon, calcium constituent enter the slag phase, as the raw material of producing cement; Elements such as plumbous zinc enter flue dust, as the raw material of zinc metallurgy, lead.The high efficiency separation and the zero release of valuable element have been realized.The product of whole flow process all obtains comprehensive reutilization, and just can obtain head product matte, slag phase and flue dust by blast furnace smelting one procedure.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Concrete embodiment:
The present invention is further illustrated below in conjunction with process flow sheet of the present invention (Fig. 1).The used ratio of material is mass percent among the embodiment.
Embodiment 1:
(main content is: Zn is 5-20% to get zinc leaching residue; Pb is 3.2-3.5%; Cd is 0.2-0.3%; Cu is 1.0%; Fe is 1.8-5%; As is 0.8-1.0%; Sb is 0.3-0.3%; Ag is 0.022-0.03%; In is 0.05-0.06%; S is 6-7%) 400kg, initial particle size-200 order accounts for 75%, allocates 10% water into, carries out briquetting then in the disk briquetting machine, obtains the zinc leaching residue nodulizing, enters the burden process section behind ventilation seasoning 10h.Get zinc kiln slag (main content is: CuO is 1.12%, and TFe is 31.36%, and Zn is 8.15%, and Ag is 119.3g/t, and In is 198.4g/t) material 46%, the initial particle size of zinc kiln slag requires+10 orders to account for 75%; The fixed carbon content of adding 15% is 74% coke, 5% SiO
2Content is the silica more than 98%, 34% zinc leaching residue nodulizing, enters blast furnace smelting after four kinds of materials adopt round stirrer mixing.The processing condition that blast furnace is controlled are: blast furnace smelting temperature distribution scope is 600～1300 ℃, and the focal area smelting temperature that requires blast furnace is greater than 1250 ℃, and melting cycle is 40min, and the air port ratio of blast furnace is 4.5%.Zinc kiln slag and zinc leaching residue behind blast furnace smelting, obtain matte mutually, flue dust mutually with slag mutually; The enrichment of matte phase copper, gold and silver-colored valuable element, adopt the copper metallurgy principle process to reclaim copper, Jin Heyin, directly as the raw material of copper metallurgy; Flue dust is rich in zinc and lead element mutually, adopts the mode of bag collection to reclaim the zinc in the flue dust, plumbous valuable element, direct raw material as zinc metallurgy, lead; Slag contains iron, silicon and calcium constituent mutually, directly as the raw material of producing cement.The chemical ingredients of matte is: Cu is 7%; Ag is the 900g/t matte; Au is the 2g/t matte.The chemical ingredients of flue dust is: Zn is 25%; Pb is 28%, and germanium is 800g/t; The chemical ingredients of slag phase is: iron level is 27%, and the content of silicon-dioxide is 30%, and calcium oxide content is 18%.
Embodiment 2:
(main content is: Zn is 5-20% to get zinc leaching residue; Pb is 3.2-3.5%; Cd is 0.2-0.3%; Cu is 1.0%; Fe is 1.8-5%; As is 0.8-1.0%; Sb is 0.3-0.3%; Ag is 0.022-0.03%; In is 0.05-0.06%; S is 6-7%) 400kg, initial particle size-200 order accounts for 75%, allocates 15% water into, carries out briquetting then in the disk briquetting machine, obtains the zinc leaching residue nodulizing, enters the burden process section behind ventilation seasoning 14h.Get zinc kiln slag (main content is: CuO is 1.12%, and TFe is 31.36%, and Zn is 8.15%, and Ag is 119.3g/t, and In is 198.4g/t) material 53%, the initial particle size of zinc kiln slag requires+10 orders to account for 85%; The fixed carbon content of adding 15% is 74% coke, 4% SiO
2Content is the silica more than 98%, 28% zinc leaching residue nodulizing, enters blast furnace smelting after four kinds of materials adopt round stirrer mixing.The processing condition that blast furnace is controlled are: blast furnace smelting temperature distribution scope is 600～1300 ℃, and the focal area smelting temperature that requires blast furnace is greater than 1250 ℃, and melting cycle is 60min, and the air port ratio of blast furnace is 5.5%.Zinc kiln slag and zinc leaching residue behind blast furnace smelting, obtain matte mutually, flue dust mutually with slag mutually; The enrichment of matte phase copper, gold and silver-colored valuable element, adopt the copper metallurgy principle process to reclaim copper, Jin Heyin, directly as the raw material of copper metallurgy; Flue dust is rich in zinc and lead element mutually, adopts the mode of bag collection to reclaim the zinc in the flue dust, plumbous valuable element, direct raw material as zinc metallurgy, lead; Slag contains iron, silicon and calcium constituent mutually, directly as the raw material of producing cement.The chemical ingredients of matte is: Cu is 8%; Ag is the 1000g/t matte; Au is the 3g/t matte.The chemical ingredients of flue dust is: Zn is 28%; Pb is 32%, and germanium is 900g/t; The chemical ingredients of slag phase is: iron level is 24%, and the content of silicon-dioxide is 33%, and calcium oxide content is 17%.
Embodiment 3:
(main content is: Zn is 5-20% to get zinc leaching residue; Pb is 3.2-3.5%; Cd is 0.2-0.3%; Cu is 1.0%; Fe is 1.8-5%; As is 0.8-1.0%; Sb is 0.3-0.3%; Ag is 0.022-0.03%; In is 0.05-0.06%; S is 6-7%) 400kg, initial particle size-200 order accounts for 75%, allocates 20% water into, carries out briquetting then in the disk briquetting machine, obtains the zinc leaching residue nodulizing, enters the burden process section behind ventilation seasoning 16h.Get zinc kiln slag (main content is: CuO is 1.12%, and TFe is 31.36%, and Zn is 8.15%, and Ag is 119.3g/t, and In is 198.4g/t) material 60%, the initial particle size of zinc kiln slag requires+10 orders to account for 95%; The fixed carbon content of adding 15% is 74% coke, 2% SiO
2Content is the silica more than 98%, 23% zinc leaching residue nodulizing, enters blast furnace smelting after four kinds of materials adopt round stirrer mixing.The processing condition that blast furnace is controlled are: blast furnace smelting temperature distribution scope is 600～1300 ℃, and the focal area smelting temperature that requires blast furnace is greater than 1250 ℃, and melting cycle is 80min, and the air port ratio of blast furnace is 6.1%.Zinc kiln slag and zinc leaching residue behind blast furnace smelting, obtain matte mutually, flue dust mutually with slag mutually; The enrichment of matte phase copper, gold and silver-colored valuable element, adopt the copper metallurgy principle process to reclaim copper, Jin Heyin, directly as the raw material of copper metallurgy; Flue dust is rich in zinc and lead element mutually, adopts the mode of bag collection to reclaim the zinc in the flue dust, plumbous valuable element, direct raw material as zinc metallurgy, lead; Slag contains iron, silicon and calcium constituent mutually, directly as the raw material of producing cement.The chemical ingredients of matte is: Cu is 9%; Ag is the 1300g/t matte; Au is the 5g/t matte.The chemical ingredients of flue dust is: Zn is 30%; Pb is 35%, and germanium is 950g/t; The chemical ingredients of slag phase is: iron level is 21%, and the content of silicon-dioxide is 35%, and calcium oxide content is 15%.
Claims (1)
1. the method with blast furnace while melting zinc leaching residue and zinc kiln slag comprises briquetting, batching, melting and smelted product treatment process, it is characterized in that the ratio that adopts in present method is mass percent, and concrete steps are as follows:
A. get a certain amount of zinc leaching residue and 10～20% water mix naturally, the initial particle size of zinc leaching residue requires-200 orders to account for more than 70%, carries out briquetting then in the disk briquetting machine, obtains the zinc leaching residue nodulizing, and is standby behind ventilation seasoning 10-16h;
B. get zinc kiln slag 46～60%, initial particle size requires+10 orders to account for more than 75%; Allocate zinc leaching residue nodulizing 22～34%, coke 15%, silica 2～5% into; Enter melting in the blast furnace after four kinds of mixing of materials;
C. mixture carries out the processing condition of blast furnace smelting and is: the blast furnace smelting temperature is 600～1300 ℃, and melting cycle is 40～80min, and the air port of blast furnace is 4.5～6.1% than distribution scope;
D. zinc kiln slag and zinc leaching residue behind blast furnace smelting, obtain matte mutually, flue dust mutually with slag mutually; Matte adopts the copper metallurgy principle process to reclaim copper, Jin Heyin mutually, direct raw material as copper metallurgy; The mode of bag collection that flue dust adopts mutually reclaims the zinc in the flue dust, plumbous valuable element, direct raw material as zinc metallurgy, lead; Slag is mutually directly as the raw material of producing cement.
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| CN102628103A (en) * | 2012-02-23 | 2012-08-08 | 永兴县华鑫铅锡有限责任公司 | Method for enriching valuable metal from mine tailing and smelting slag by fire method |
| CN103468954B (en) * | 2013-08-16 | 2016-08-17 | 云南云铜锌业股份有限公司 | A kind of zinc kiln slag, leached mud and lead skim carry out the method that valuable metal is reclaimed in melting |
| CN103710544B (en) * | 2013-12-18 | 2015-12-02 | 昆明理工大学科技产业经营管理有限公司 | A kind of method of valuable metal synthetical recovery in zinc smelting dreg |
| CN105420499A (en) * | 2015-09-22 | 2016-03-23 | 天津仁新玻璃材料有限公司 | Co-disposal method for zinc oxide leaching residues and waste cathode ray tube (CRT) cone glass |
| CN106148715A (en) * | 2016-08-01 | 2016-11-23 | 江苏省冶金设计院有限公司 | Process the method and system of leaded zinc kiln slag |
| CN106086400A (en) * | 2016-08-01 | 2016-11-09 | 江苏省冶金设计院有限公司 | Process the method and system of lead Zn scrap returns |
| CN111204981B (en) * | 2020-01-18 | 2022-04-01 | 河北博泰环保科技有限公司 | Direct oxygen blowing melting process of secondary kiln slag and method for preparing microcrystalline glass |
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| JP3539334B2 (en) * | 1999-03-30 | 2004-07-07 | Ｊｆｅスチール株式会社 | Recovery method of zinc in dust |
| CN100482816C (en) * | 2007-09-24 | 2009-04-29 | 昆明理工大学 | Method for reclaiming valuable element from zinc kiln slag |
| CN101338373B (en) * | 2008-08-14 | 2011-05-18 | 上饶市华丰铜业有限公司 | Method for producing smelting copper-cobalt oxidation ore by blast furnace |
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