CN106148712A - A kind of method carrying bismuth from the white flue dust of Copper making - Google Patents

A kind of method carrying bismuth from the white flue dust of Copper making Download PDF

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Publication number
CN106148712A
CN106148712A CN201610683869.XA CN201610683869A CN106148712A CN 106148712 A CN106148712 A CN 106148712A CN 201610683869 A CN201610683869 A CN 201610683869A CN 106148712 A CN106148712 A CN 106148712A
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China
Prior art keywords
bismuth
flue dust
concentration
electrodeposition
white
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CN201610683869.XA
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Chinese (zh)
Inventor
张焕然
林泓富
衷水平
陈杭
苏秀珠
王俊娥
吴健辉
熊家春
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Zijin Mining Group Co Ltd
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Zijin Mining Group Co Ltd
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Priority to CN201610683869.XA priority Critical patent/CN106148712A/en
Publication of CN106148712A publication Critical patent/CN106148712A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02Working-up flue dust
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a kind of method carrying bismuth from the white flue dust of Copper making, it is with white flue dust as raw material, through sulfuric acid leaching remove impurity, sulphuric acid and sodium chloride potassium cloride bismuth, utilize sodium hydroxide carry out chlorine oxygen bismuth precipitation, by concentrated hydrochloric acid configuration five operations such as electric effusion and bismuth electrodeposition after directly obtain standard cathode bismuth plate.A kind of method carrying bismuth from the white flue dust of Copper making of the present invention has that technological process is short, simple to operate, high efficiency, low cost, free of contamination feature, solve current white dust treatment and bismuth extracts the problems such as process complexity, complex operation, working environment difference, it is achieved that the short route of Copper making process associated metal and high-efficiency resource recycling.

Description

A kind of method carrying bismuth from the white flue dust of Copper making
Technical field
The present invention relates to non-ferrous metal hydrometallurgy field, be specifically related to a kind of employing eddy flow electrodeposition process from Copper making Between short flow high efficiency carries bismuth in the white flue dust of product method.
Background technology
During copper pyrometallurgy, converter electric precipitator dusts is referred to as white flue dust.In converter for copper matte converting process, part has valency Element such as lead, zinc, bismuth etc. are all enriched in white flue dust, different according to Copper making raw material, each essential element and content in white flue dust It is respectively as follows: copper 2 ~ 5%, lead 15 ~ 20%, zinc 8 ~ 10%, bismuth 10 ~ 15%.Therefore, it is many that white flue dust has valuable metal kind, and content is high Feature, be a kind of METAL EXTRACTION resource with higher economic worth.Bismuth is a kind of environmental protection, be worth and higher have coloured gold Belong to, be widely used in the fields such as quasiconductor, superconductor, fire retardant, pigment, cosmetics, chemical reagent, electronic ceramics.
At present, commonly used white flue dust puies forward bismuth technique: white flue dust pelletizing → melting → lead bismuth alloy → alloy electrolysis → rich bismuth earth of positive pole fusing → refinement oxide arsenic removal, antimony → zincification desilver → logical chlorine except zinc, lead → add alkali dechlorinate high temperature refinery → Essence bismuth (99.95%).The defect existed is this technological process length, complex operation, and whole process relates to thermal process, smelting process Noxious fume discharge capacity is big, production environment is poor.
Sun Baohui etc. (CN201510867122.5) propose a kind of Whote-wet method and reclaim copper, the method for zinc in white flue dust, but not Relate to the extraction to bismuth.Blue bluish waves etc. (CN201510010375.0) are pointed out to use bismuth in the white flue dust of potassium cloride, and precipitate chlorine Oxygen bismuth, but still use tradition fire refining process with chlorine oxygen bismuth for raw material refine bismuth, only reach raising working performance purpose.Deng Tao Eddy flow electrodeposition process is directly used to produce bismuth meal or standard the moon Deng (CN201310281176.4) from monomer bismuth mineral chloridizing leach solution Pole bismuth plate, considers the most comprehensive on electrolytic deposition process foreign ion on the impact of bismuth product.
Summary of the invention
It is an object of the invention to provide that a kind of technological process is short, simple to operate, high efficiency, low cost, free of contamination from Copper making The method carrying bismuth in white flue dust, solve current white dust treatment and bismuth to extract process complexity, complex operation, working environment poor Etc. problem, to realize the short route of Copper making process associated metal, high-efficiency resource recycling.
For realizing object above, a kind of method of bismuth that carries from the white flue dust of Copper making of the present invention with white flue dust as raw material, warp Standard cathode bismuth is directly obtained after sulfuric acid leaching remove impurity, potassium cloride bismuth, chlorine oxygen bismuth precipitation, electric effusion configuration and bismuth electrodeposition operation Plate, concrete operation step is as follows:
One, sulfuric acid leaching remove impurity: with white flue dust as raw material, the liquid-solid ratio controlling sulphuric acid and white flue dust is (3 ~ 7): 1, sulfuric acid concentration 20 ~ 70g/L, extraction temperature 50 ~ 85 DEG C, filters after leaching 0.5 ~ 2h;
Two, potassium cloride bismuth: with the leached mud of step one as raw material, controls the liquid-solid ratio of sulphuric acid, sodium chloride solution and leached mud For (3 ~ 6): 1, sulfuric acid concentration 50 ~ 100g/L, sodium chloride concentration 150 ~ 300g/L, filter after being stirred at room temperature leaching 1 ~ 3h, Realize the leaching of bismuth;
Three, chlorine oxygen bismuth precipitation: be 2 than the regulation of sodium hydroxide that concentration is 10 ~ 20% to pH value through quality by the leachate of step 2 ~ 3, filter after ageing 0.5 ~ 1h, obtain chlorine oxygen bismuth precipitation;
Four, electric effusion configuration: with the chlorine oxygen bismuth of step 3 gained as raw material, uses quality than the concentrated hydrochloric acid that concentration is 38% to it Dissolve configuration electric effusion, the bismuth concentration 50 ~ 80g/L of this electric effusion, concentration of hydrochloric acid 10 ~ 15g/L;
Five, bismuth electrodeposition: carry out eddy flow electrodeposition with electric effusion prepared by step 4, electric effusion is squeezed into airtight under circulating pump effect Eddy flow Winning cell electrodeposition carries bismuth, electrodeposition temperature 30 ~ 60 DEG C, and electric current density controls 400 ~ 1000A/m2, electrodeposition time 2 ~ 5h, obtain Negative electrode bismuth plate;Step 4 configuration electric effusion is returned when electric effusion bi concns is less than 10g/L.
The liquid that the present invention relates to is volume mass ratio, i.e. liquid employing volume with the liquid-solid ratio of solid, and solid uses Quality, Unit/mL/g.
A kind of above-mentioned method carrying bismuth from the white flue dust of Copper making has the advantages that
(1) use leaching-eddy flow electrodeposition process to carry bismuth, shorten the white flue dust of tradition and propose bismuth technological process, simple to operate, improve Production efficiency;
(2) bismuth refine tradition firing method process is improved to Whote-wet method flow process, it is to avoid toxic and harmful during thermal process, Dust emission, optimizes working environment.
Detailed description of the invention
Make the most in detail below in conjunction with the detailed description of the invention method carrying bismuth from the white flue dust of Copper making a kind of to the present invention Describe in detail bright.
A kind of method of bismuth that carries from the white flue dust of Copper making of the present invention is with white flue dust as raw material, through sulfuric acid leaching remove impurity, bismuth Directly obtain standard cathode bismuth plate after potassium cloride, chlorine oxygen bismuth precipitation, electric effusion configuration and bismuth electrodeposition, be exemplified below four enforcements Example, concrete operation step and the technological parameter of each embodiment are as follows:
Embodiment one
With cupric 2.5%, lead 14.7%, zinc 8.5%, bismuth 10.2% white flue dust as raw material, control the liquid-solid ratio of sulphuric acid and white flue dust 3:1, sulfuric acid concentration 60g/L, extraction temperature 65 DEG C, extraction time 0.5h, copper, zinc removal efficiency are respectively 83.7%, 95.1%;
With leached mud as raw material, controlling sulphuric acid, sodium chloride solution is 3:1 with the liquid-solid ratio of leached mud, sulfuric acid concentration 60g/L, chlorine Changing na concn 150g/L, be stirred at room temperature leaching 1h, bismuth leaching rate reaches 95.7%;
Leachate use quality than concentration be 10% sodium hydroxide regulation terminal pH be 2, ageing 0.5 after be filtrated to get chlorine oxygen bismuth;
Chlorine oxygen bismuth uses quality to dissolve than the concentrated hydrochloric acid that concentration is 38%, controls bismuth concentration 50g/L, terminal concentration of hydrochloric acid 10g/L is as electric effusion;
Electric effusion carries out eddy flow electrodeposition, and bismuth solution eddy flow electrolytic deposition process controls electrodeposition temperature 35 DEG C, and electric current density controls 450A/ m2, electrodeposition time 2h, obtain standard cathode bismuth plate, the bismuth response rate reaches 93.2%.
Embodiment two
With cupric 4.3%, lead 16.2%, zinc 9%, bismuth 11% white flue dust as raw material, control liquid-solid ratio 4:1 of sulphuric acid and white flue dust, Sulfuric acid concentration 60g/L, extraction temperature 55 DEG C, leach 0.5h, copper, zinc removal efficiency are respectively 88.2%, 94.7%;
With leached mud as raw material, the liquid-solid ratio controlling sulphuric acid, sodium chloride solution and leached mud is 4:1, sulfuric acid concentration 60g/L, chlorine Leaching 1.5h is stirred at room temperature under conditions of changing sodium 150g/L, and bismuth leaching rate reaches 96.2%;
Leachate uses quality to be 2.5 than the sodium hydroxide regulation terminal pH that concentration is 10%, filters, obtain chlorine oxygen after ageing 0.5 Bismuth;
Chlorine oxygen bismuth uses quality to dissolve than the concentrated hydrochloric acid that concentration is 38%, controls bismuth concentration 60g/L, terminal concentration of hydrochloric acid 10g/L is as electric effusion;
Electric effusion carries out eddy flow electrodeposition, and bismuth solution eddy flow electrolytic deposition process controls electrodeposition temperature 35 DEG C, and electric current density controls 550A/ m2, electrodeposition time 2h obtains standard cathode bismuth plate, and the bismuth response rate reaches 95.2%.
Implement three: with cupric 1.5%, lead 20.5%, zinc 11%, bismuth 13.4% white flue dust as raw material, control sulphuric acid and white cigarette Liquid-solid ratio 5:1 of dirt, sulfuric acid concentration 70g/L, extraction temperature 75 DEG C, leach 1.5h, copper, zinc removal efficiency be respectively 82.6%, 97.2%;
With leached mud as raw material, the liquid-solid ratio controlling sulphuric acid, sodium chloride solution and leached mud is 5:1, sulfuric acid concentration 70g/L, chlorine Leaching 1.5h is stirred at room temperature under conditions of changing sodium 250g/L, and bismuth leaching rate reaches 97.4%;
Leachate uses quality to be 2.8 than the sodium hydroxide regulation terminal pH that concentration is 10%, is filtrated to get chlorine oxygen bismuth after ageing 1;
Chlorine oxygen bismuth uses quality to dissolve than the concentrated hydrochloric acid that concentration is 38%, controls bismuth concentration 80g/L, terminal concentration of hydrochloric acid 15g/L is as electric effusion;
Electric effusion carries out eddy flow electrodeposition, and bismuth solution eddy flow electrolytic deposition process controls electrodeposition temperature 50 C, and electric current density controls 800A/ m2, electrodeposition time 2h obtains standard cathode bismuth plate, and the bismuth response rate reaches 97%.
Implement four: with cupric 2.1%, lead 19.2%, zinc 5.3%, bismuth 15.8% white flue dust as raw material, control sulphuric acid and white cigarette Liquid-solid ratio 7:1 of dirt, sulfuric acid concentration 70g/L, extraction temperature 80 DEG C, leach 3h, copper, zinc removal efficiency are respectively 85.6%, 86.9%;
With leached mud as raw material, the liquid-solid ratio controlling sulphuric acid, sodium chloride solution and leached mud is 5:1, sulfuric acid concentration 80g/L, chlorine Leaching 3h is stirred at room temperature under conditions of changing sodium 300g/L, and bismuth leaching rate reaches 99.2%;
Leachate uses quality to be 3 than the sodium hydroxide regulation terminal pH that concentration is 10%, is filtrated to get chlorine oxygen bismuth after ageing 1;
Chlorine oxygen bismuth uses quality to dissolve than the concentrated hydrochloric acid that concentration is 38%, controls bismuth concentration 80g/L, terminal concentration of hydrochloric acid 15g/L is as electric effusion;
Electric effusion carries out eddy flow electrodeposition, and bismuth solution eddy flow electrolytic deposition process controls electrodeposition temperature 30 DEG C, and electric current density controls 1000A/ m2, electrodeposition time 1.5h obtains standard cathode bismuth plate, and the bismuth response rate reaches 98.7%.
Above four embodiments of contrast, the comprehensive technical indexes of embodiment three is best, is most preferred embodiment.
It should be pointed out that, the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, exist Without departing from the principles of the invention, it is also possible to improved according to the above description or modify, all these improvement or modification All should fall in the protection domain of the claims in the present invention.

Claims (1)

1. the method carrying bismuth from the white flue dust of Copper making, is characterized in that: it, with white flue dust as raw material, removes through sulfuric acid leaching Miscellaneous, potassium cloride bismuth, chlorine oxygen bismuth precipitation, electric effusion configure and directly obtain standard cathode bismuth plate after bismuth electrodeposition operation, specifically grasp Make step as follows:
One, sulfuric acid leaching remove impurity: with white flue dust as raw material, the liquid-solid ratio controlling sulphuric acid and white flue dust is (3 ~ 7): 1, sulfuric acid concentration 20 ~ 70g/L, extraction temperature 50 ~ 85 DEG C, filters after leaching 0.5 ~ 2h;
Two, potassium cloride bismuth: with the leached mud of step one as raw material, controls the liquid-solid ratio of sulphuric acid, sodium chloride solution and leached mud For (3 ~ 6): 1, sulfuric acid concentration 50 ~ 100g/L, sodium chloride concentration 150 ~ 300g/L, filter after being stirred at room temperature leaching 1 ~ 3h, Realize the leaching of bismuth;
Three, chlorine oxygen bismuth precipitation: be 2 than the regulation of sodium hydroxide that concentration is 10 ~ 20% to pH value through quality by the leachate of step 2 ~ 3, filter after ageing 0.5 ~ 1h, obtain chlorine oxygen bismuth precipitation;
Four, electric effusion configuration: with the chlorine oxygen bismuth of step 3 gained as raw material, uses quality than the concentrated hydrochloric acid that concentration is 38% to it Dissolve configuration electric effusion, the bismuth concentration 50 ~ 80g/L of this electric effusion, concentration of hydrochloric acid 10 ~ 15g/L;
Five, bismuth electrodeposition: carry out eddy flow electrodeposition with electric effusion prepared by step 4, electric effusion is squeezed into airtight under circulating pump effect Eddy flow Winning cell electrodeposition carries bismuth, electrodeposition temperature 30 ~ 60 DEG C, and electric current density controls 400 ~ 1000A/m2, electrodeposition time 2 ~ 5h, obtain Negative electrode bismuth plate;Step 4 configuration electric effusion is returned when electric effusion bi concns is less than 10g/L.
CN201610683869.XA 2016-08-18 2016-08-18 A kind of method carrying bismuth from the white flue dust of Copper making Pending CN106148712A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107746975A (en) * 2017-11-14 2018-03-02 河南中原黄金冶炼厂有限责任公司 A kind of method that high content chlorine oxygen bismuth is reclaimed in the flue dust acid leaching residue from Copper making
CN108624759A (en) * 2018-04-16 2018-10-09 北京科技大学 A method of the comprehensively recovering valuable metal from white cigarette dirt
CN108754167A (en) * 2018-06-28 2018-11-06 北京矿冶科技集团有限公司 A kind of method that Copper making flue dust efficiently separates copper arsenic

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CN103397182A (en) * 2013-07-05 2013-11-20 浙江科菲冶金科技股份有限公司 Method for efficiently recycling bismuth from monomer bismuth ore
JP2015214760A (en) * 2015-07-30 2015-12-03 住友金属鉱山株式会社 Method for treating copper refining dust

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107746975A (en) * 2017-11-14 2018-03-02 河南中原黄金冶炼厂有限责任公司 A kind of method that high content chlorine oxygen bismuth is reclaimed in the flue dust acid leaching residue from Copper making
CN108624759A (en) * 2018-04-16 2018-10-09 北京科技大学 A method of the comprehensively recovering valuable metal from white cigarette dirt
CN108624759B (en) * 2018-04-16 2020-06-05 北京科技大学 Method for comprehensively recovering valuable metals from white smoke
CN108754167A (en) * 2018-06-28 2018-11-06 北京矿冶科技集团有限公司 A kind of method that Copper making flue dust efficiently separates copper arsenic

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