CN102321804A - Wet separation technology for material containing lead, bismuth and molybdenum - Google Patents
Wet separation technology for material containing lead, bismuth and molybdenum Download PDFInfo
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- CN102321804A CN102321804A CN201110296797A CN201110296797A CN102321804A CN 102321804 A CN102321804 A CN 102321804A CN 201110296797 A CN201110296797 A CN 201110296797A CN 201110296797 A CN201110296797 A CN 201110296797A CN 102321804 A CN102321804 A CN 102321804A
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- bismuth
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- molybdenum
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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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Abstract
The invention relates to a wet separation technology for a material containing lead, bismuth and molybdenum, belonging to the technical field of nonferrous metallurgy. The material containing lead, bismuth and molybdenum provided by the invention comprises the following steps of: firstly carrying out ball milling on the material containing lead, bismuth and molybdenum, pulping by adding pure alkaline and an oxidant, and leaching out a pulping material liquid by heating, so that molybdenum exists in a leaching liquid in the form of sodium molybdenum, and lead bismuth silver copper iron slag is formed for lead, bismuth, silver, copper and iron remaining in leached slag; dissolving lead by hydrochloric acid deposition part of leachate, forming lead slag, smelting and recycling by a lead fire method, then adding calcium chloride, and depositing calcium molybdate; leaching out the lead bismuth silver copper iron slag by sulfate, sodium chloride and hydrogen peroxide, and separating Pb in the form of silver and lead slag; and depositing the bismuth in the liquid after lead deposition through hydrolysis, thus the separation of lead, bismuth and molybdenum is realized. According to the invention, the metal recovery rate is high, the separation effect is good, the waste liquid is recycled, no waste slag is produced, and the technology is environmentally-friendly and safe.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, relate in particular to a kind of wet separation technology of leaded bismuth molybdenum material.
Background technology
Handle plumbous molybdenum ore (wulfenite) in prior art and adopt wet processing usually, adopt firing method process to handle plumbous bismuth molybdenum ore material usually rarely to report and handle plumbous bismuth mineral material.The leaded bismuth molybdenum material that company purchased, its staple content is: Pb:35.81%, Bi:13.08%, Mo:10.17%, S:0.8%, Ag:0.53%, Fe:1.5%, Cu:0.58%.The many metalliferous materials of bismuth-containing for this kind complicated component comprehensively recycle; If adopt the pyrorefining flow process; Can cause the molybdenum loss excessive, smart bismuth is smelted not up to standard, influences the recovery of plumbous bismuth molybdenum and the purification of metal product; Make flow process complicated, therefore be necessary in time to work out a kind of novel process to address the above problem:
On September 5th, 2007; Jinwang Industry Co., Ltd., Hunan's Wang Zhixiong, Wu Zuxiang, wear the disclosed Chinese invention patent application publication number of gorgeous equality people CN 101029353A; " the comprehensive technology of extracting valuable metal from the many metalliferous materials of bismuth-containing "; Its method is from the many metalliferous materials of bismuth-containing, to leach copper, tellurium with sulfuric acid with chlorizating agent and oxygenant bismuth metal also to be drained out again, and Ag is with the AgCl form, and Pb is with PbSO
4, PbCl
2In the form slag, desilver from leached mud in leach liquor, adds ammoniacal liquor adjust pH to 1.5 earlier, obtains the bismuth oxychloride slag of bismuth-containing 70%, and this bismuth slag becomes thick bismuth or directly is processed into pure bismuthous oxide bismuth trioxide with pyrometallurgical smelting, and in the leach liquor, copper and ammoniacal liquor complexing do not deposit, and use Na
2CO
3Transfer pH to 4.5, heavy tellurium gets tellurous oxide, obtains copper-containing solution at last, with cupric electrolysis output cupric greater than 90% copper powder.
On October 4th, 2000; By the disclosed Chinese invention patent application publication number of people CN 1268579A " new process for treating electrolytic anode mud " such as the Zhang Xu of Kunming University of Science and Technology, Liu Zhonghuas is a kind of non-ferrous metal wet extraction process; Adopt the wet processing process of sulfuric acid system require great effort copper, nickel, bismuth, silver in the electrolysis anode sludge; Under the effect of pressure positive atmospheric pressure oxidation of 500 ㎜ water columns and catalyzer; Make copper get into liquid, wherein antimony, bismuth turn to oxide compound, lead is converted into lead sulfate, and silver is converted into silver suboxide and gets into; Concentration 95-100 ℃, catalyzer are made up of ferrous sulfate, nitric acid, hydrochloric acid, nitrite or nitrate, and leach liquor is got arsenical copper slag and displaced liquid in return with iron, and the displaced liquid crystallisation by cooling obtains ferrous sulfate, and mother liquor returns oxidation and leaches.
On July 12nd, 2006; Henan, the effluent south plumbous Zhai Ju of limited-liability company of gold such as pays at the disclosed Chinese invention patent application publication number of people CN 1800421A; " valuable metal reclaims technology in the thick bismuth ", this process using wet method, pyrogenic process combine and carry out the comprehensive recovery of valuable metal.At first material is carried out water, ball milling, wash and filter, obtain antimony lead slag liquid, after the antimony lead slag that produces returns pyrogenic process system recoveries antimony, plumbous smelting system, institute's production fluid is with copper sponge displacement Ag output gold and silver wherein, and the output gold and silver returns the precious metal smelting system.To the liquid of displacement behind the gold and silver heavy bismuth that is hydrolyzed, filtration is drained out liquid use iron powder replacement Cu, heavy Cu output copper sponge, the liquid adding lime behind the heavy Cu neutralizes, and post precipitation discharges.
Summary of the invention
Of the present invention will dealing with problems is to overcome the deficiency that exists in the prior art, proposes a kind of wet separation technology of leaded bismuth molybdenum material, and this technology utilization Wet-process metallurgy method metal recovery rate is high; Good separating effect; The waste liquid recycle, no waste residue output, Environmental Safety.
Technical thinking of the present invention is such; Leaded bismuth molybdenum material adds soda ash and oxygenant slurrying earlier through ball milling, the leaching of heating of slurrying feed liquid; Molybdenum is present in the leach liquor with the Sodium orthomolybdate form, and lead, bismuth, silver, copper and iron are stayed and are formed plumbous bismuth silver copper scum in the leached mud; Leach liquor is partly dissolved lead with hydrochloric acid acidizing and precipitation, forms lead skim and reclaims with plumbous pyrometallurgical smelting, adds calcium chloride again, is settled out calcium molybdate; Above-mentioned leaded bismuth silver copper scum leaches with sulfuric acid, sodium-chlor, ydrogen peroxide 50, and Pb is with the isolated in form of argentalium slag; Heavy plumbous back liquid is through the heavy bismuth of hydrolysis; Thereby realize the separation of lead, bismuth, molybdenum.The back liquid of above-mentioned separating treatment lead, bismuth, molybdenum all can return ball milling slurrying after treatment and use, or does open circuit and handle.
The concrete technical scheme that the present invention deals with problems is following:
A kind of wet separation technology of leaded bismuth molybdenum material, its step is following
A with the leaded bismuth molybdenum of bulk material through being crushed to particle line footpath less than 3 ㎝;
The material of b after fragmentation is through the wet-type ball mill ball milling, and the control raw meal particle size reaches-100 orders;
C wet ball-milling material adds soda ash and ydrogen peroxide 50 slurrying; It is 5M that slurrying adds soda ash concentration, and ydrogen peroxide 50 adds by inventory 5%;
D slurrying material pumps into leaching vat, and control liquid-solid ratio 3:1 heats up 90～95 ℃, leaches insulation 2-3h;
E filters the extract in the d step, gets plumbous bismuth silver copper scum; Leach liquor use hydrochloric acid adjust pH is 6 (salt acidifyings), and deposition is partly dissolved the heavy lead skim of plumbous formation, and press filtration gets lead skim and send the pyrogenic process refining to reclaim lead; Pressing filtering liquid adjust pH again is 7, adds calcium chloride heating, temperature keeping 1-2h, and the calcium chloride add-on is 1.5 times of theoretical amount, and water sampling is surveyed molybdenum less than 100mg/l, crosses and filters the calcium molybdate throw out that contains molybdenum 23%, dry packaging and warehousing;
The post precipitation liquid that f forms in the e step returns first section slurrying usefulness, or discharging after treatment;
G adds sulfuric acid, sodium-chlor, ydrogen peroxide 50 in the plumbous bismuth silver copper scum that above-mentioned e step is leached; Bismuth metal is leached, and copper and ferrous metal also get in the solution simultaneously; Cross and filter heavy plumbous back liquid, Pb is with PbSO
4Form, Ag is with AgCl
2Form stay in the argentalium slag; In this step, leach the sulfuric acid concentration that uses and be 4M, CI in the sodium-chlor
-Concentration is 4M, and ydrogen peroxide 50 is pressed 8% of metal weight of material and added, and extraction temperature is 90～95 ℃, extraction time 5h;
H adds in the liquid caustic soda and regulates pH in the liquid of the heavy plumbous back of g step is 1.5, makes the form hydrolysis of bismuth with chlorine oxygen bismuth; Filter bismuth oxychloride slag, propose the bismuth deep processing with pyrometallurgical smelting; Liquid behind the filtering heavy bismuth, crystallisation by cooling are separated out and are returned the c step usefulness of sizing mixing behind the vitriol again;
Behind the heavy bismuth that i forms in the h step in the liquid, if gather detrimental impurity A s greater than 50mg/l, Fe adds the ferrous sulfate neutralization with lime and makes the foreign metal deposition during greater than 100mg/l, handles waste water and returns the c step usefulness of sizing mixing again; Or do open circuit and handle.
The theoretical amount of calcium chloride add-on is in the above-mentioned steps, presses the stoichiometry of the needed calcium chloride of molybdenum element participation chemical reaction generation calcium molybdate in the solution.
The present invention utilizes hydrometallurgy, and from the wet separation recovery valuable metal of leaded bismuth molybdenum material, prior art has following advantage relatively:
1, metal recovery rate is high; The present invention can reach main metallic lead and goes into the slag rate more than 89% in force; Main bismuth metal is gone into the slag rate more than 82%; Main metal molybdenum is gone into the slag rate more than 92%, and silver-bearing copper is gone into slag with plumbous bismuth, and the argentalium slag that is produced, bismuth slag and calcium molybdate are the desirable feedstock of extracting lead, bismuth, molybdenum; Help the next procedure treating product, added value is high.
2 the present invention do not have the waste residue output, but the most of waste water of qualified discharge can return use, Environmental Safety after only a small amount of waste water was crossed processing.The present invention removes extraction temperature and requires more than 90 ℃, other reaction heat all capable of using and waste heat reaction, consumes energy in addition.
Description of drawings
Figure is a process flow sheet of the present invention.
Embodiment
Embodiment below in conjunction with accompanying drawing is concrete is described the present invention;
The bismuth-containing material that this embodiment adopts, concrete composition is following:
Pb:35.81%，Bi：13.08%，Mu：10.58%，S：0.8%，Ag：0.53%，Fe：1.5%，Cu：0.58%；
This material is that refinery's waste residue becomes bulk, after cracking metalluster is arranged, and what value was higher in the material is bismuth and molybdenum, and other reclaims from sub product.
The process step such as the accompanying drawing of wet separation valuable metal from above-mentioned leaded bismuth molybdenum material.
A with the leaded bismuth molybdenum of bulk material through being crushed to particle line footpath less than 3 ㎝;
The material of b after cracking is through the wet-type ball mill ball milling, and control also can be that 100% raw meal particle size reaches-100 more than 85%;
C wet ball-milling material adds soda ash and ydrogen peroxide 50 slurrying; It is 5M that slurrying adds soda ash concentration, and ydrogen peroxide 50 adds by inventory 5%;
D slurrying material pumps into leaching vat, and control liquid-solid ratio 3:1 heats up 90～95 ℃, leaches insulation 2-3h;
The extract of e in the d step filters, and gets plumbous bismuth silver copper scum; Plumbous bismuth silver copper scum is used in addition.The leach liquor adjust pH is 6 (salt acidifyings), forms heavy lead skim, filters; Lead skim send pyrometallurgical smelting of lead usefulness, and the leach liquor adjust pH is 7, adds calcium chloride heating, temperature keeping 1-2h; The calcium chloride add-on is 1.5 times of theoretical amount; Water sampling is surveyed molybdenum less than 100mg/l, crosses and filters calcium molybdate throw out, dry packaging and warehousing;
The waste liquid that f forms in the e step returns first section leaching after treatment and uses;
G adds sulfuric acid, sodium-chlor, ydrogen peroxide 50 in the plumbous bismuth silver copper scum that above-mentioned e step is leached; Bismuth metal is leached, and copper and ferrous metal also get in the solution simultaneously; Cross and filter heavy plumbous back liquid, Pb is with PbSO
4Form, Ag is with AgCl
2Form stay in the argentalium slag; In this step, leach the sulfuric acid concentration that uses and be 4M, CI in the sodium-chlor
-Concentration is 4M, and ydrogen peroxide 50 is pressed 8% of metal weight of material and added, and extraction temperature is 90～95 ℃, extraction time 5h;
H adds in the liquid caustic soda and regulates pH in the liquid of the heavy lead back of g step is 1.5, makes the form hydrolysis of bismuth with chlorine oxygen bismuth, while portion C u, and Fe also can get in the bismuth oxychloride slag, filters bismuth oxychloride slag, proposes the bismuth deep processing with pyrometallurgical smelting; Liquid behind the filtering heavy bismuth, crystallisation by cooling are separated out and are returned the c step usefulness of sizing mixing behind the vitriol again;
Behind the heavy bismuth that i forms in the h step in the liquid, if gather detrimental impurity A s greater than 50mg/l, Fe adds the ferrous sulfate neutralization with lime and makes the foreign metal deposition during greater than 100mg/l, handles waste water and returns the c step usefulness of sizing mixing again; Or do open circuit and handle.
Liquid adds the c step usefulness of sizing mixing after treatment behind the heavy bismuth that in the h step, forms, and re-uses after needing crystallisation by cooling to separate out vitriol, and used lime adds ferrous sulfate method makes the foreign metal deposition, and makes discharged wastewater met the national standard.
Claims (1)
1. the wet separation technology of a leaded bismuth molybdenum material, it is characterized in that: step is following:
A with the leaded bismuth molybdenum of bulk material through being crushed to particle line footpath less than 3 ㎝;
The material of b after fragmentation is through the wet-type ball mill ball milling, and the control raw meal particle size reaches-100 orders;
C wet ball-milling material adds soda ash and ydrogen peroxide 50 slurrying; It is 5M that slurrying adds soda ash concentration, and ydrogen peroxide 50 adds by inventory 5%;
D slurrying material pumps into leaching vat, and control liquid-solid ratio 3:1 heats up 90～95 ℃, leaches insulation 2-3h;
E filters the extract in the d step, gets plumbous bismuth silver copper scum; Leach liquor use hydrochloric acid adjust pH is 6, and deposition is partly dissolved the heavy lead skim of plumbous formation, and press filtration gets lead skim and send the pyrogenic process refining to reclaim lead; Pressing filtering liquid adjust pH again is 7, adds calcium chloride heating, temperature keeping 1-2h, and the calcium chloride add-on is 1.5 times of theoretical amount, and water sampling is surveyed molybdenum less than 100mg/l, crosses and filters the calcium molybdate throw out that contains molybdenum 23%, dry packaging and warehousing;
The post precipitation liquid that f forms in the e step returns first section slurrying usefulness, or discharging after treatment;
G adds sulfuric acid, sodium-chlor, ydrogen peroxide 50 in the plumbous bismuth silver copper scum that above-mentioned e step is leached; Bismuth metal is leached, and copper and ferrous metal also get in the solution simultaneously; Cross and filter heavy plumbous back liquid, Pb is with PbSO
4Form, Ag is with AgCl
2Form stay in the argentalium slag; In this step, leach the sulfuric acid concentration that uses and be 4M, CI in the sodium-chlor
-Concentration is 4M, and ydrogen peroxide 50 is pressed 8% of metal weight of material and added, and extraction temperature is 90～95 ℃, extraction time 5h;
H adds in the liquid caustic soda and regulates pH in the liquid of the heavy plumbous back of g step is 1.5, makes the form hydrolysis of bismuth with chlorine oxygen bismuth, filters bismuth oxychloride slag, proposes the bismuth deep processing with pyrometallurgical smelting; Liquid behind the filtering heavy bismuth, crystallisation by cooling are separated out and are returned the c step usefulness of sizing mixing behind the vitriol again;
Behind the heavy bismuth that i forms in the h step in the liquid, if gather detrimental impurity A s greater than 50mg/l, Fe adds the ferrous sulfate neutralization with lime and makes the foreign metal deposition during greater than 100mg/l, handles waste water and returns the c step usefulness of sizing mixing again; Or do open circuit and handle.
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| CN201110296797A CN102321804A (en) | 2011-09-30 | 2011-09-30 | Wet separation technology for material containing lead, bismuth and molybdenum |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965499A (en) * | 2012-11-01 | 2013-03-13 | 湖南有色金属研究院 | Method for extracting valuable element in arsenic salt purification slag from zinc hydrometallurgy |
| CN109762995A (en) * | 2019-04-01 | 2019-05-17 | 东北大学 | A method of molybdenum element in recycling nickel base superalloy waste cut materials |
| CN113774220A (en) * | 2020-06-09 | 2021-12-10 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum, bismuth and vanadium from waste catalysts of acrylic acid, methacrylic acid and esters thereof |
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| JP2002018395A (en) * | 2000-07-06 | 2002-01-22 | Taiheiyo Cement Corp | Treating method for waste |
| CN101225474A (en) * | 2007-10-15 | 2008-07-23 | 肇庆市大鸿明贵金属有限公司 | Precious metals smelting method for anode sludge or nonferrous smelting slag |
| CN102051478A (en) * | 2010-11-28 | 2011-05-11 | 郴州市金贵银业股份有限公司 | Wet process for treating lead copper matte |
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2011
- 2011-09-30 CN CN201110296797A patent/CN102321804A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018395A (en) * | 2000-07-06 | 2002-01-22 | Taiheiyo Cement Corp | Treating method for waste |
| CN101225474A (en) * | 2007-10-15 | 2008-07-23 | 肇庆市大鸿明贵金属有限公司 | Precious metals smelting method for anode sludge or nonferrous smelting slag |
| CN102051478A (en) * | 2010-11-28 | 2011-05-11 | 郴州市金贵银业股份有限公司 | Wet process for treating lead copper matte |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965499A (en) * | 2012-11-01 | 2013-03-13 | 湖南有色金属研究院 | Method for extracting valuable element in arsenic salt purification slag from zinc hydrometallurgy |
| CN109762995A (en) * | 2019-04-01 | 2019-05-17 | 东北大学 | A method of molybdenum element in recycling nickel base superalloy waste cut materials |
| CN113774220A (en) * | 2020-06-09 | 2021-12-10 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum, bismuth and vanadium from waste catalysts of acrylic acid, methacrylic acid and esters thereof |
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Application publication date: 20120118 |