CN104846216B - Treatment method of complex copper-molybdenum ore - Google Patents
Treatment method of complex copper-molybdenum ore Download PDFInfo
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- CN104846216B CN104846216B CN201510206089.1A CN201510206089A CN104846216B CN 104846216 B CN104846216 B CN 104846216B CN 201510206089 A CN201510206089 A CN 201510206089A CN 104846216 B CN104846216 B CN 104846216B
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Abstract
The invention discloses a treatment method of complex copper-molybdenum ore, belonging to the technical field of wet metallurgy. The method comprises the following steps: adding proper amount of sulfuric acid and additive into copper-molybdenum ore to make pressure leaching so as to make copper and others be leached into the solution, and the molybdenum still remains in the leached slag in the form of molybdenum sulfide. The leached residue is roasted or pressurized and oxidized to produce molybdenum oxide and other products, and the leached liquid, copper sulfate solution, is replaced with iron powder to produce sponge copper or extracted to produce copper sulfate, electrolytic copper and other products. The invention provides a convenient and rapid molybdenum and copper separation method, which improves the grade of molybdenum concentrate, reduces the impurity content of products and comprehensively recovers copper.
Description
Technical field
The present invention relates to a kind of processing method of the high complicated copper-molybdenum of copper content, obtain making high-copper low while copper products
Grade molybdenum concntrate is changed into the high-grade molybdenum concntrate that suitable molybdenum is smelted.
Background technology
Copper and molybdenum are that molybdenum and copper are generally association in important nonferrous metal resource, nature, and copper-molybdenum is deposited extensively in China
With very high economic value.Using the molybdenum concntrate and copper concentrate that ore-dressing technique output is qualified more than traditional copper-molybdenum, strict control
Copper content in molybdenum concntrate processed.After the fired production molybdenum oxide of molybdenum concntrate, further production molybdenum-iron or ammonia leaching produces ammonium molybdate.Molybdenum
MoS in concentrate roasting process2It is oxidized to MoO3, when copper content is higher, the molybdate of indissoluble is easily generated, molybdenum is had a strong impact on
The rate of recovery.But the qualified molybdenum concntrate of the more difficult sorting outputs of some copper-molybdenums, for ensure copper-molybdenum the rate of recovery can only output copper-molybdenum mix
Ore deposit is closed, it is more difficult to handled using traditional handicraft, in the urgent need to developing a kind of new copper-molybdenum smelting process.
Except traditional pyrometallurgical smelting, the smelting process for cupric molybdenite is also based on the pressure leaching of molybdenite at present
Technique.For example：Pressurize alkaline leaching, under certain temperature and pressure, and molybdenum enters solution with soluble molybdate, and copper because
Stayed in for its slightly solubility in mineral, be to realize copper-cobalt ore the characteristics of this flow, equipment corrosion is small, reaction is gentle, still
Quantity of alkali consumption is big, and the reaction time is long, and a large amount of sodium sulphate of generation are more intractable, and production cost is high；Pressurize acidic leaching, certain
Under temperature and pressure, most copper enter solution in the form of copper sulphate, and about more than 20% molybdenum enters solution, remaining molybdenum with
The form of molybdic acid is present among solid phase, and the total conversion of molybdenum is up to 99%, but Copper in Slag is of a relatively high, and Molybdenum in Solution and copper do not have
Efficiently separate, cause smelting cost to increase.
The content of the invention
The purpose of the present invention be for a kind of the not enough there is provided processing method of high copper-molybdenum concentrate of above-mentioned treatment technology, this
The purpose of invention is achieved through the following technical solutions.
A kind of processing method of complicated copper-molybdenum, it is characterised in that comprise the following steps：
(1) fine grinding：By the complicated copper-molybdenum fine grinding；
(2) copper is leached in advance：Copper-molybdenum after step (1) fine grinding is leached by leaching agent pressure oxidation, cupric leaching is obtained
Go out solution and low copper-molybdenum concentrate, realize the separation of copper and molybdenum, copper enters leachate, and molybdenum is enriched with leached mud；
(3) copper is reclaimed：Copper is reclaimed in the cupric infusion solution processing that step (2) is obtained；
(4) molybdenum is reclaimed：Molybdenum is reclaimed in the low copper-molybdenum concentrate processing that step (3) is obtained.
Further, the leaching agent described in step (2) mixes for the one or more in the inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid
Acid is closed, the preferred 5-200g/L of initial acid of leaching, extraction temperature is 80-200 DEG C, and liquid-solid ratio is 2-10:1, extraction time
For 0.5-5 hours, the partial pressure of oxygen of leaching was 2-10 standard atmospheric pressure, and appropriate lignosulphonates are added during leaching prevents the bag of sulphur
Wrap up in, the addition of lignosulphonates is usually the 0.2%-0.5% of copper-molybdenum.
The method that the present invention is provided, copper leaches that step is higher to the degree of oxidation of copper in advance, and the leaching of copper can be realized substantially, and
The degree of oxidation of molybdenum is relatively low, and molybdenum is still still in solid phase with the form of molybdenite, iron according to the difference of initial acidity leach into
Enter solution or entered with the forms such as siderotil, bloodstone precipitation in slag.
Further, step (2) adds additive and promotes to react progress, and to improve the leaching rate of copper, the additive is
Carbonaceous material, addition is the 0-10% of copper-molybdenum.
Further, the carbonaceous material, the one or more in coal dust, coke or activated carbon.
Further, step (3) reclaims the method for copper for displacement or extracted.Leachate can be through iron powder (bits, plate) displacement
Produce copper sponge, or extraction production copper sulphate/electrolytic copper product.
Displacement is, using displacement reaction, to be cemented out the copper in solution using cheap iron powder, the technique is simply easy
OK, but product copper sponge need to be processed further handle or sell outside.
Leachate is extracted using the extractant such as grades of Lix 984, pure copper-bath is obtained, evaporative crystallization is obtained
Electrolytic copper product is obtained to sulfuric acid copper products or electro-deposition.
Further, it is that work is leached in calcining molybdenum ore concentrate-ammonia soaking technology or pressure oxidation that step (4), which reclaims the method for molybdenum,
Skill.
Calcining molybdenum ore concentrate-ammonia soaking technology be molybdenum smelt traditional handicraft, the fired molybdenum made in molybdenum disulfide of molybdenum concntrate with
Sulphur is separated, and changes into the molybdenum trioxide for being soluble in ammoniacal liquor, and molybdenum trioxide and ammoniacal liquor generation ammonium molybdate enter solution, reach leaching
The purpose gone out, but the technique is suitable to processing standard molybdenum concntrate, has limitation for copper-molybdenum.
It is to utilize appropriate oxidant in aqueous that pressure oxidation, which is leached, generally air or oxygen, is made in molybdenum concntrate
Sulphur be oxidized to sulfate radical and enter aqueous phase, molybdenum is then oxidized to MoO4 2-(alkaline medium) or H2MoO4(acid medium) enter aqueous phase or
Solid phase.Because the technique is carried out under conditions of HTHP, when handling copper-molybdenum, the copper and part molybdenum in ore are equal
Into solution, separating treatment need to be carried out in subsequent handling.And the present invention is under the conditions of relatively mild, to carry out the pre- place of selectivity
Reason, while leaching copper and molybdenum is not leached, the separation of the two is realized, while making molybdenum be enriched with slag.
When step (3) reclaims copper using extraction, copper raffinate can be used as step (4) molybdenum pressure oxidation leaching agent；Step
(4) when reclaiming molybdenum using pressure oxidation extract technology, molybdenum pressureleaching solution can presoak copper step after carrying molybdenum as step (2)
Leaching agent.Recycled by above-mentioned, make full use of material, reduce discharge.
Further, the leaching rate of copper is more than 80% in step (2), and the leaching rate of molybdenum is below 5%.
Further, the complicated copper-molybdenum is the molybdenum ore of cupric more than 3%.
Further, the copper-molybdenum particle diameter after step (1) fine grinding accounts for more than 90% below 300 mesh.
In the present invention unless otherwise indicated beyond, ratio, percentage are mass ratio.
The method provided by the present invention, can effectively solve the problems, such as the synthetical recovery of complicated copper-molybdenum, simplify technique stream
Journey, is easy to production operation, it is easy to accomplish industrialization, effectively realizes the separation of copper-molybdenum.
Brief description of the drawings
The schematic flow sheet for the copper-molybdenum processing that accompanying drawing provides for the present invention.
Embodiment
For the clearer explanation present invention, following instance is enumerated, but it is without any restrictions to the scope of the present invention.
The embodiment of the present invention provides a kind of schematic diagram of the processing method of complicated copper-molybdenum, such as accompanying drawing institute
Show, its principle is to be leached the copper in mineral in the form of copper sulphate using condition of high voltage, and molybdenum is still stayed with the form of sulfide
In solid phase, leached mud further reclaims molybdenum.
Leachate can be through iron powder (bits, plate) displacement production copper sponge, or extraction production copper sulphate/electrolytic copper product.Use metal
Iron replaces the leachate of cupric, and it is 0-100 DEG C, reaction time 15min-24h to keep solution temperature.
Embodiment 1
Take copper-molybdenum composite ore 100g, main component is copper 10.63%, molybdenum 30.16%, iron 11.63%, S35 .4%, carefully
It is milled to below 300 mesh and accounts for 90%, adds the dilute sulfuric acid pulp that 500ml concentration is 100g/L, 0.2g lignins are added, at 150 DEG C
Lower progress pressure oxidation leaching, during be passed through oxygen, control partial pressure of oxygen 5atm, react 2 hours.
After reaction terminates, copper and iron etc. is leached into solution, and the leaching rate such as copper, iron reaches more than 85%, slag containing molybdenum 45% with
On.Filtered fluid adds iron replacement copper, and the purity of copper sponge is 89.35%.Copper ashes pressure oxidation molybdenum at 150~220 DEG C is soaked,
Molybdenum conversion ratio reaches more than 98%.
Embodiment 2
The dilute sulfuric acid for being 25g/L by 100g copper-molybdenums addition 500ml concentration, addition 5g coal dusts, copper-molybdenum cupric 8.35%,
Molybdenum 35.67%, 150 DEG C of controlling reaction temperature, partial pressure of oxygen 5atm, extraction time 3h.
After the completion of reaction, copper leaching rate more than 90%, iron partly precipitated enters in leached mud, and molybdenum leaching rate is less than 2%.
Copper, extraction of copper more than 98% are extracted into the extraction of above-mentioned solution.The pressurized Oxidation Leaching molybdenum of leached mud, molybdenum conversion ratio
More than 98.5%.
Claims (8)
1. a kind of processing method of complicated copper-molybdenum, it is characterised in that the complicated copper-molybdenum sorts for the difficult of cupric more than 3%
Molybdenum ore, comprises the following steps：
(1) fine grinding：By the complicated copper-molybdenum fine grinding；
(2) copper is leached in advance：Copper-molybdenum after step (1) fine grinding is leached by leaching agent pressure oxidation, cupric leaching is obtained molten
Liquid and low copper-molybdenum concentrate；Leaching agent is one or more mixed acid in sulfuric acid, nitric acid, hydrochloric acid inorganic acid, the initial acid of leaching
Concentration is 5-200g/L, and extraction temperature is 80~200 DEG C, and liquid-solid ratio is 2~10:1, extraction time is 0.5~5 hour, is leached
Partial pressure of oxygen be 2-10 standard atmospheric pressure, appropriate lignosulphonates are added during leaching；
(3) copper is reclaimed：Copper is reclaimed in the cupric infusion solution processing that step (2) is obtained；
(4) molybdenum is reclaimed：Molybdenum is reclaimed in the low copper-molybdenum concentrate processing that step (3) is obtained.
2. the method as described in claim 1, it is characterised in that step (2) adds additive and promotes reaction to carry out, the addition
Agent is carbonaceous material, and addition is the 0~10% of copper-molybdenum.
3. method as claimed in claim 2, it is characterised in that the carbonaceous material, in coal dust, coke or activated carbon
It is one or more.
4. the method as described in claim 1, it is characterised in that step (3) reclaims the method for copper for displacement or extracted.
5. the method as described in claim 1, it is characterised in that it is calcining molybdenum ore concentrate-ammonia leaching work that step (4), which reclaims the method for molybdenum,
Skill or pressure oxidation extract technology.
6. the method as described in claim 1, it is characterised in that the leaching rate of copper is more than 80% in step (2), the leaching of molybdenum
Rate is below 5%.
7. the method as described in claim 1, it is characterised in that step (3) reclaims copper using extraction, copper raffinate is used as step
Suddenly (4) molybdenum pressure oxidation leaching agent；Step (4) reclaims molybdenum using pressure oxidation extract technology, and molybdenum pressureleaching solution is after carrying molybdenum
The leaching agent of copper step is presoaked as step (2).
8. the method as described in claim 1, it is characterised in that the copper-molybdenum particle diameter after step (1) fine grinding is below 300 mesh
Account for more than 90%.
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| CN105907992B (en) * | 2016-06-28 | 2018-08-31 | 西北有色金属研究院 | A kind of method that pressure oxidation detaches molybdenum, copper and rhenium in Low Grade Molybdenum Concentrates |
| CN108342591B (en) * | 2018-02-11 | 2019-12-20 | 眉山顺应动力电池材料有限公司 | New method for separating molybdenum and copper |
| CN111560518B (en) * | 2020-07-01 | 2022-01-28 | 长沙有色冶金设计研究院有限公司 | Treatment method of copper-containing molybdenum concentrate |
| CN112831660B (en) * | 2020-12-30 | 2022-09-13 | 成都虹波钼业有限责任公司 | Process for comprehensively utilizing molybdenum ore leaching slag |
| CN114164349A (en) * | 2022-02-11 | 2022-03-11 | 矿冶科技集团有限公司 | Method for removing impurities from molybdenum ore with high copper content and performing closed circulation on solution |
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| US3714325A (en) * | 1970-11-17 | 1973-01-30 | Us Interior | Recovery of molybdenite |
| CN101537388B (en) * | 2009-04-21 | 2011-09-07 | 广州有色金属研究院 | Separation method for bismuth-molybdenum-copper-sulfide mixed concentrate |
| CN102634675B (en) * | 2012-04-28 | 2013-11-06 | 中南大学 | Method for treating copper-molybdenum mixed ores |
| CN103194617B (en) * | 2013-04-23 | 2014-01-15 | 昆明理工大学 | Method for strengthening agitation leaching of cuprite red copper ore type copper oxide |
| CN103526013B (en) * | 2013-10-23 | 2016-01-20 | 北京矿冶研究总院 | Comprehensive recovery method of complex molybdenum sulfide ore |
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