CN103484694A - Method for extracting bismuth from copper-bismuth concentrate - Google Patents

Method for extracting bismuth from copper-bismuth concentrate Download PDF

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Publication number
CN103484694A
CN103484694A CN201310372427.XA CN201310372427A CN103484694A CN 103484694 A CN103484694 A CN 103484694A CN 201310372427 A CN201310372427 A CN 201310372427A CN 103484694 A CN103484694 A CN 103484694A
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China
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bismuth
copper
heavy
leaching
extracting
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CN201310372427.XA
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李元昌
李畅
尹久发
陈学元
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Research & Design Institute Of Yunnan Tin Industry Group Inc
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Research & Design Institute Of Yunnan Tin Industry Group Inc
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    • 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 relates to a method for extracting bismuth from copper-bismuth concentrate. The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for extracting bismuth by leaching copper-bismuth-molybdenum minerals. The technical scheme is as follows: the method comprises the following steps: mixing and stirring copper-bismuth-molybdenum minerals containing 4-14 wt% of bismuth for leaching while keeping the pH value of the solution at 0.3-0.6; stirring the leach solution with CaCO3 used as a neutralizer to precipitate bismuth; sending the precipitate to the next mineral separation or smelting process to obtain bismuth oxochloride and valuable metals; carrying out oxidation de-ironing and sulfuric acid calcium removal on the bismuth precipitation solution; and returning the obtained purified solution to the leaching step for cyclic use. The method can extract bismuth from copper-bismuth-molybdenum minerals more simply and effectively, so that the bismuth can be well separated from other metals. The method has the advantages of low production cost, high efficiency, high safety and reliability and no environment pollution.

Description

A kind of method of extracting bismuth from copper bismuth concentrate
Technical field
The invention belongs to technical field of wet metallurgy, be specifically related to a kind of method that copper bismuth molybdenum ore extracts bismuth that leaches.
Background technology
At occurring in nature, the form with free metal and mineral exists bismuth, and mineral have bismuthinite, bismite etc.Although pyrometallurgical smelting exists SO 2pollution problem, but for bismuth mineral of high grade, that composition is single, be still at present the main method that bismuth is smelted.And low-grade bismuth concentrate, bismuth chats, low-grade sulphide ores that complicated difficult is selected adopt the reverberatory furnace pyrometallurgical smelting, not only the rate of recovery is low, and is difficult to refining output high-quality essence bismuth.The later stage sixties 20th century, China starts to be devoted to the research of bismuth mineral hydrometallurgy new process, formed with iron trichloride and made leaching agent, leach bismuth in the acid chlorine salt system, make bismuth in mineral enter solution with the form of bismuth Chloro complex, by iron replacement output sponge bismuth, through pyrorefining, produce smart bismuth.
In recent years, many R&D institutions both domestic and external form according to the difference of bismuth sulfide ore in succession, around reducing operating cost, solve environmental pollution, the enrichment problem of valuable metal concentration in the regeneration of iron trichloride and solution, many new hydrometallurgy flow processs have been studied, the heavy bismuth method of leach-hydrolysis of iron trichloride leaching-iron replacement method, iron trichloride leaching-diaphragm electrodeposition method, iron trichloride, chlorine gas selecting lixiviation process, hydrochloric acid nitrous acid system etc.
Above-mentioned several method has all been used iron trichloride or chlorine, use iron trichloride to have the Fe(II) problem of regeneration, the Fe(II) will use chlorine in the time of regeneration Fe(III), the use of chlorine has not only improved cost but also has existed very large safety problem.The use of electrolysis and iron powder etc. also allows technical process more complicated, complex operation, and cost increase etc. has produced many new problems.
The heavy bismuth method of new chlorination-hydrolysis, Tang Motang etc. have proposed a kind of Wet-process metallurgy method of new processing bismuth concentrate on the basis of research for many years---and the bismuth method is sunk in new chlorination hydrolysis.At the temperature of 36~378K, adopt two sections circulating leachings, greatly improved the leaching rate of recovery of bismuth.The characteristics of this flow process are to have adopted a kind of acidic aqueous solution that contains metal chloride (A#CA), it has the advantage of iron trichloride and chlorinated with chlorine agent concurrently, solved the circulation accumulation problem of iron in the regeneration of leaching agent and solution, and the bi concns in solution is improved greatly, the corresponding expanded of the throughput of subsequent handling.
Although the heavy bismuth method of this new chlorination-hydrolysis has improved the rate of recovery of bismuth, solved the problems such as circulation accumulation of iron in the regeneration of leaching agent and solution, also exist problem in actual production, because it needs heating, need to use chlorine, this has increased cost, has reduced security; Although leaching yield is higher, simultaneously a lot of precious metals are also immersed out, make its part enter leach liquor, and part is stayed in slag, make the comprehensive reutilization of precious metal become difficult.
Summary of the invention
The purpose of this invention is to provide a kind of method of extracting bismuth from copper bismuth concentrate, can extract bismuth from copper bismuth molybdenum ore more simply and effectively, make bismuth can be good at separating with other metal, production cost is low, and efficiency is high, safe and reliable, free from environmental pollution.
Realize that the technical scheme that above-mentioned purpose of the present invention is taked is: the mixed in hydrochloric acid agitation leach that is 28~32% by the copper bismuth molybdenum ore of bismuth-containing 4~14wt% and concentration makes pH remain on 0.3~0.6, then uses CaCO 3as neutralizing agent, leach liquor is stirred to heavy bismuth, throw out enters next step ore dressing or smelts flow process and obtain chlorine oxygen bismuth and valuable metal, and heavy bismuth liquid carries out iron removal by oxidation and sulfuric acid deliming successively, and the scavenging solution obtained returns to the leaching operation and recycles.
The technical scheme that the present invention further takes is: 1. the leaching liquid-solid ratio of copper bismuth molybdenum ore and hydrochloric acid is 2.7~3.3:1ml/g, and hydrochloric acid adds in the dropping mode, passes into pneumatic blending reaction 4~6 hours; 2. leach liquor first adopts raw ore to carry out pre-neutralization, during pre-neutralization, keep the pH value to be controlled at 1.2~1.5, pre-neutralization can effectively utilize the residual acid of liquid after Leaching in Hydrochloric Acid, reduce the alkalescence of raw ore, improve the pH value of solution, the consumption of minimizing neutralizing agent in next step heavy bismuth process, the quality of raising chlorine oxygen bismuth; 3. the leach liquor after pre-neutralization starts heavy bismuth again, and initially heavy bismuth pH>=1.8, control pH=3.0 when heavy bismuth completes; 4. heavy bismuth liquid CaCO 3for neutralizing agent regulator solution pH carries out the deironing purification 3.3~3.7, scavenging solution reaches iron content 5~8g/L and gets final product.
Technical scheme of the present invention also comprises that 1. copper bismuth molybdenum ore should be crushed to granularity 180~220 orders; 2. whole leaching and in and operation all remain under normal temperature, normal pressure and carry out; 3. during Han Tie in liquid after heavy bismuth<=8g/L, no longer carry out above-mentioned deironing and deliming operation, directly turn back to and leach operation and use.
the invention has the beneficial effects as follows: by bismuth-containing, higher copper bismuth molybdenum ore extracts bismuth by leaching at normal temperatures and pressures with solution, and the liquid after leaching is regulated pH value after by pre-treatment and sunk bismuth acquisition chlorine oxygen bismuth product.Slag enters beneficiation flowsheet or smelts flow process.Its technique is simple, and flow process is short, and solution can recycle, does not have waste water to discharge.Do not use chlorine oxidation Fe(II in solution) regeneration Fe(III).So production cost is low, efficiency is high, safe and reliable, free from environmental pollution.Can avoid the wet processing long flow path, reagent dosage is large, leaches poor selectivity, a large amount of strippings of impurity, and the valuable metals such as gold and silver disperse, and part enters leach liquor, and part enters the problems such as slag, comprehensive reutilization difficulty.Effectively bismuth is extracted from the copper bismuth mineral, polymetallic ore is effectively separated, improved productivity effect.
The accompanying drawing explanation
Fig. 1 is principle process flow sheet of the present invention.
Specific embodiments
embodiment 1
The copper bismuth molybdenum ore composition of bismuth-containing: Bi 9.69%, and Cu 0.75%, Fe24.14 %, and Ca10.16%, Mo0.654%, be milled to 180 purpose granularities.
In the situation of normal temperature and pressure blowing air, the hydrochloric acid soln that is 28% by the concentration of preparation joins in container, then copper bismuth molybdenum ore is added in container and stirs 6 hours, and adds hydrochloric acid in the dropping mode, makes pH remain on 0.3, obtains leach liquor.According to the bismuth-containing amount in liquid, use CaCO 3as neutralizing agent, leach liquor is stirred to heavy bismuth.Liquid after the heavy bismuth of filtration, the leached mud obtained is dried, and heavy bismuth liquid carries out iron removal by oxidation and sulfuric acid deliming successively, and the scavenging solution obtained returns to the leaching operation and recycles.Leached mud is 0.25wt% containing Bi, and leaching yield is 95.2%.
embodiment 2
The copper bismuth molybdenum ore composition Bi 5.28% of bismuth-containing, Cu0.45 %, Fe 18.24%, and Ca 8.25%, and Mo 0.542%, is milled to 200 purpose granularities.
In the situation of normal temperature and pressure blowing air, the hydrochloric acid soln that is 31% by the concentration of preparation joins in container, then copper bismuth molybdenum ore is added in container and stirs 5 hours, and adds hydrochloric acid in the dropping mode, makes pH remain on 0.5, obtains leach liquor.According to the bismuth-containing amount in liquid, use CaCO 3as neutralizing agent, leach liquor is stirred to heavy bismuth.Liquid after the heavy bismuth of filtration, the leached mud obtained is dried, and heavy bismuth liquid carries out iron removal by oxidation and sulfuric acid deliming successively, and the scavenging solution obtained returns to the leaching operation and recycles.Leached mud is 0.24wt% containing Bi, and leaching yield is 94.9%.
embodiment 3
The copper bismuth molybdenum ore composition of bismuth-containing: Bi 13.62%, and Cu 0.84%, and Fe 23.15%, and Ca 9.6%, and Mo 0.58%, is milled to 220 purpose granularities.
In the situation of normal temperature and pressure blowing air, the hydrochloric acid soln that is 32% by the concentration of preparation joins in container, then copper bismuth molybdenum ore is added in container and stirs 4 hours, and adds hydrochloric acid in the dropping mode, makes pH remain on 0.6, obtains leach liquor.According to the bismuth-containing amount in liquid, use CaCO 3as neutralizing agent, leach liquor is stirred to heavy bismuth.Liquid after the heavy bismuth of filtration, the leached mud obtained is dried, and heavy bismuth liquid carries out iron removal by oxidation and sulfuric acid deliming successively, and the scavenging solution obtained returns to the leaching operation and recycles.Leached mud is 0.28wt% containing Bi, and leaching yield is 95.8%.

Claims (3)

1. a method of extracting bismuth from the copper bismuth mineral, is characterized in that: by the copper bismuth molybdenum ore of bismuth-containing 4~14wt% and the mixed in hydrochloric acid agitation leach of concentration 28~32%, make pH remain on 0.3~0.6, then use CaCO 3as neutralizing agent, leach liquor is stirred to heavy bismuth, throw out enters next step ore dressing or smelts flow process and obtain chlorine oxygen bismuth and valuable metal, and heavy bismuth liquid carries out iron removal by oxidation and sulfuric acid deliming successively, and the scavenging solution obtained returns to the leaching operation and recycles.
2. the method for extracting bismuth from the copper bismuth mineral according to claim 1, it is characterized in that: 1. the leaching liquid-solid ratio of copper bismuth molybdenum ore and hydrochloric acid is 2.7~3.3:1ml/g, and hydrochloric acid adds in the dropping mode, passes into pneumatic blending and reacts 4~6 hours; 2. leach liquor first adopts raw ore to carry out pre-neutralization, during pre-neutralization, keeps the pH value to be controlled at 1.2~1.5; 3. the leach liquor after pre-neutralization starts heavy bismuth again, and initially heavy bismuth pH>=1.8, control pH=3.0 when heavy bismuth completes; 4. heavy bismuth liquid CaCO 3for neutralizing agent regulator solution pH carries out the deironing purification 3.3~3.7, scavenging solution reaches iron content 5~8g/L and gets final product.
3. the method for extracting bismuth from the copper bismuth mineral according to claim 2, it is characterized in that: 1. copper bismuth molybdenum ore should be crushed to granularity 180~220 orders; 2. whole leaching and in and operation all remain under normal temperature, normal pressure and carry out; 3. during Han Tie in liquid after heavy bismuth<=8g/L, directly turn back to and leach operation and use.
CN201310372427.XA 2013-08-25 2013-08-25 Method for extracting bismuth from copper-bismuth concentrate Pending CN103484694A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108441629A (en) * 2018-04-20 2018-08-24 中南大学 A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder
CN108559841A (en) * 2018-04-20 2018-09-21 中南大学 A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product
CN108611503A (en) * 2018-04-20 2018-10-02 中南大学 A kind of method that oxygen pressure decomposes wolframite and prepares tungsten oxide and tungsten powder
CN108642276A (en) * 2018-04-20 2018-10-12 中南大学 A kind of method that acid decomposition scheelite prepares tungsten oxide and tungsten powder
CN108640156A (en) * 2018-04-20 2018-10-12 中南大学 A method of preparing tungsten oxide and tungsten powder from scheelite
CN108796220A (en) * 2018-07-04 2018-11-13 湖南工业大学 A kind of method of extraction-vulcanization phase inversion separation of Bismuth and iron in bismuth iron mixed solution

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CN101376929A (en) * 2008-09-27 2009-03-04 中南大学 Method for extracting bismuth from bismuth ore concentrate or material containing bismuth
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CN101376929A (en) * 2008-09-27 2009-03-04 中南大学 Method for extracting bismuth from bismuth ore concentrate or material containing bismuth
CN101403045A (en) * 2008-11-17 2009-04-08 河南豫光金铅股份有限公司 Synthetic recovery method for plumbum anode slime slag rich in bismuth
JP2013155432A (en) * 2012-01-31 2013-08-15 Mitsubishi Materials Corp Recovery method of bismuth

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108441629A (en) * 2018-04-20 2018-08-24 中南大学 A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder
CN108559841A (en) * 2018-04-20 2018-09-21 中南大学 A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product
CN108611503A (en) * 2018-04-20 2018-10-02 中南大学 A kind of method that oxygen pressure decomposes wolframite and prepares tungsten oxide and tungsten powder
CN108642276A (en) * 2018-04-20 2018-10-12 中南大学 A kind of method that acid decomposition scheelite prepares tungsten oxide and tungsten powder
CN108640156A (en) * 2018-04-20 2018-10-12 中南大学 A method of preparing tungsten oxide and tungsten powder from scheelite
CN108796220A (en) * 2018-07-04 2018-11-13 湖南工业大学 A kind of method of extraction-vulcanization phase inversion separation of Bismuth and iron in bismuth iron mixed solution

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