CN106345607A - Beneficiation and metallurgy combined process for processing refractory copper and zinc ores - Google Patents
Beneficiation and metallurgy combined process for processing refractory copper and zinc ores Download PDFInfo
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- CN106345607A CN106345607A CN201610768147.4A CN201610768147A CN106345607A CN 106345607 A CN106345607 A CN 106345607A CN 201610768147 A CN201610768147 A CN 201610768147A CN 106345607 A CN106345607 A CN 106345607A
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- zinc
- copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a beneficiation and metallurgy combined process for processing refractory copper and zinc ores. The process is a 'flotation-acid leaching' beneficiation and metallurgy combined process and includes the steps: obtaining copper and zinc bulk concentrates from refractory copper and zinc sulfide ores by the aid of a flotation method; directly performing acid agitation leaching for flotation concentrates to efficiently separate copper and zinc. The beneficiation and metallurgy combined process has the advantages that content of zinc in copper concentrates can be remarkably reduced, so that grades of the copper concentrates are improved, and comprehensive utilization of the zinc in the copper and zinc sulfide ores is achieved. The beneficiation and metallurgy combined process is simple, efficient, good in continuity, easy to implement and high in recovery rate, and popularization and application are facilitated in industrial production of the refractory copper and zinc ores.
Description
Technical field
The present invention relates in non-ferrous metal field sulphide ore technique of preparing, particularly a kind of novel dressing and smelting united
Process difficultly-selected copper zinc ore technology.
Background technology
Copper zinc vulcanizing mine stone is the important source material of copper smelting zinc, originates in skarn type, hot-liquid type or hydrothermal filling and metasomatism more
In type mineral deposit.Mineral composition is complex, and ore structures are also complicated, generally dissemination type and compact massive type.Copper zinc vulcanizing mine
Due to mineral densification symbiosis, disseminated grain size is thin, needs fine grinding that them just can be made to reach monomer dissociation, but crossing of fine grinding generation is pulverized
Phenomenon makes floatation process deteriorate, and the specific surface area of ore particle increases, and the solubility of copper mineral increases simultaneously, and in ore pulp, copper ion increases
Many, sphalerite becomes due to the activation by copper ion easily to float, simultaneously because containing a large amount of pyrite and magnetic in copper zinc mineral
The mineral such as pyrite and sludge, cause Flotation separation of copper from zinc difficult.
With the day by day minimizing easily selecting copper-zinc ore resource, complicated difficultly-selected copper zinc polymetallic ore becomes important Ore money
Source.The mineral disseminated grain size of some Cu-Zn complex ore is thin, and have mutually contains in emulsion droplet shape；Copper mine species are various, and floatability differs；Contain
There are the more secondary pig copper and soluble heavy metal salt, so that sphalerite is activated, lead to copper-znic separation effect on driving birds is not good.Traditional
Processing method is " protect copper and lose zinc ", i.e. output copper concentrate after ore dressing, and zinc is then present in copper concentrate as impurity element,
Cause the very big wasting of resources.Copper concentrate when selling due to reason need to be lived together as button containing zinc is higher, also have impact on further through
Ji benefit.It can be seen that, difficultly-selected copper zinc Ore is processed using traditional ore-dressing technique, copper-znic separation is difficult, metal recovery rate is relatively low.Right
Similar difficultly-selected copper zinc Ore carry out efficiently, environmental protection develop and use, it has also become the important technological problems that ore dressing worker faces.
Therefore, it is necessary to develop a kind of new technique, can such difficultly-selected copper zinc Ore of effective process, realize copper zinc resource
High efficiente callback utilize.
Content of the invention
The difficulty existing for difficult copper-zinc ore assorting room, the present invention proposes a kind of the dressing and smelting united of novelty
Process difficultly-selected copper zinc ore technology, this technique to copper zinc sulfuration raw ore carry out copper zinc mix choosing on the basis of, with hydrometallurgy
Method separation copper and zinc, on the one hand reduce the content of zinc metal in copper concentrate, thus improve the quality of copper concentrate, the opposing party
Face avoids the waste of zinc resource, solves the comprehensive utilization of zinc resource.Selecting smelting combination technique tends to simple making ore dressing process
While, substantially increase metal recovery rate, the smelting overall recovery that selects of copper zinc metal all increases, and preferably achieves
The resource comprehensive utilization of copper zinc mixing sulfuration raw ore utilizes.
Selecting smelting combination new technology proposed by the present invention is achieved by the following technical solution.
A kind of selecting smelting combination new technology processing difficultly-selected copper zinc Ore, the method initially with flotation obtains copper zinc mixing essence
Ore deposit, carries out acidleach leaching, realizes copper Zn-Ca series and separates, forms " flotation-acidleach " selecting smelting combination technique.
Method for floating of the present invention is that copper zinc vulcanizing mine stone is carried out ore grinding, and the ore pulp that ore grinding obtains obtains after flotation
Copper and zinc bulk concentrate and mine tailing.
Copper in described copper zinc vulcanizing mine stone is mainly in Ore presented in chalcopyrite and secondary copper sulfide
Zinc mineral is mainly sphalerite.
Described method for floating is that copper zinc vulcanizing mine stone is carried out ore grinding, and the ore pulp that ore grinding obtains is through " one roughing-rough concentrate
- triple cleaning-of regrinding is scanned twice " flow process obtains copper and zinc bulk concentrate and mine tailing after sorting.
Acidleach leaching is that flotation copper and zinc bulk concentrate is placed in leaching tanks, adds concentrated sulphuric acid and is stirred soaking
Go out, obtain leachate, leachate carries out solid-liquid separation, leached mud be high-quality copper concentrate, cupric>20%, contain zinc<5%, leaching
Go out liquid lean solution and recycle formation rich solution, more purified, concentrate, crystallisation by cooling operation, obtain sulphuric acid zinc product.
Ore grinding pulp density of the present invention is 75～82%；Flotation pulp concentration is 25～35%；The ph value of ore pulp for 8～
10.
Its chemical composition is cu:15～20% to above-mentioned copper and zinc bulk concentrate by mass percentage, zn:8～25%, s: >
30%, remaining is gangue content and trace element.
Leaching of the present invention is carried out in acid medium.In acid medium, sphalerite surface occurs such as
Lower chemical reaction:
zns→zn2++s+2e
Although the thermodynamical equilibrium current potential of oxidation reaction is relatively low, the poor ability of sphalerite intrinsic conduction electronics.Therefore,
The dynamical resistance of oxidation is larger, its oxidizing potential=thermodynamical equilibrium current potential+oxidation overpotential.This shows to dodge zinc under electronegative potential
Ore deposit surface does not have sulfur to generate, and only under high potential, sulfide just can lose electronics and becomes elemental sulfur.It is therefore possible to use
Concentrated acid and the method heating up improve the potential value leaching medium, accelerate the oxidation of sulfur and the leaching of zinc in sphalerite, thus reaching
The purpose of Selectively leaching sphalerite.
Above-mentioned copper-znic separation process, at 80～120 DEG C, sulfuric acid concentration is 40～60% (mass ratioes) to temperature control, quality
Than for 6:1～10:1, extraction time is in 2～3h.Leachate 5～30g/l containing zinc, zinc leaching rate can reach more than 70%, and
< 0.1g/l, copper leaching rate is less than 1% to leachate cupric.Above-mentioned leachate is carried out solid-liquid separation, leached mud is high-quality copper
Concentrate, leachate lean solution recycles formation rich solution, more purified, concentrate, crystallisation by cooling operation, obtain sulphuric acid zinc product, from
And realize the purpose of copper-znic separation.
The technological process that the present invention provides succinctly efficiently, seriality good, easily controllable, copper, the returning of zinc can be improved simultaneously
Yield, is conducive to popularization and application in difficult copper zinc ore commercial production.
Present disclosure is expanded on further with reference to Figure of description and embodiment.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
The copper zinc vulcanizing mine stone cupric 0.92% of the present embodiment, zinc 0.81%, lead 0.09%, sulfur 16.15%, silicon dioxide
36.86%, pick up from middle and lower reach of Yangtze River Large-scale Copper Mines.In Ore, copper sulfide mineral is mainly Chalkopyrite, secondly be class's copper mine,
Covellite and tetrahedrite, total distributive law about 81.52%；Copper oxide mineral is mainly malachite, cuprite etc..Zinc ore in Ore
Thing is mainly sphalerite, distributive law about 59.26%, is secondly zinc carbonate, a small amount of zinc sulfate, franklinite.Copper mineral and sudden strain of a muscle
Zinc ore granularity is fine, and embedding cloth relation is complex.Particularly, many parcel microfine and secondary micro- crystalline substance Chalkopyrite in sphalerite (<
5um), part copper zinc mineral is in the form output of copper zinc mixture.
Copper zinc vulcanizing mine stone through Hubei Province formula spallar coarse crushing, to roller spallar one-tenth in small, broken bits fine ore, fine ore Task-size Controlling is-
20mm.Weigh quantitative fine ore, pour in xmq-240*90 type conical ball mill, plus clear water ore grinding obtains initial ore pulp.Control
Ore grinding pulp density is 75～82%, mog -200 mesh more than 65%.The initial ore pulp that ball mill is discharged pours xfd into
Type single-trough flotating machine flotation, floatation concentration is 25～35%, the ph value of ore pulp is 8～10.Flotation z200 do collecting agent,
Jt2000 makees foaming agent, using in " one roughing-coarse concentrate regrinding-triple cleaning-scan twice " technological process flotation of ores
Copper-zinc sulphide minerals.Flotation concentrate is copper and zinc bulk concentrate, and flotation tailing enters selected sulfur operation.Flotation concentrate cupric 15～
20%th, zinc 8～25%, sulfur 25～35%, copper zinc flotation recovery rate is respectively 75～85%, 65～75%.
Copper and zinc bulk concentrate is 80～120 DEG C in temperature, and sulfuric acid concentration is 40～60% (mass ratioes), and mass ratio is 6:1
Under conditions of～10:1, it is stirred leaching 2～3 hours.Leachate 5～30g/l containing zinc, zinc leaching rate can reach 70% with
On, and leachate cupric < 0.1g/l, copper leaching rate be less than 1%.Above-mentioned leachate is carried out solid-liquid separation, leached mud is height
Quality copper concentrate, cupric>20%, contain zinc<5%.Leachate lean solution recycles formation rich solution, more purified, concentrate, cooling knot
Brilliant operation, prepares sulphuric acid zinc product." flotation-acidleach " process integration that the present invention provides, copper, the comprehensive recovery of zinc can be distinguished
Reach 75～85%, 50～65% it is achieved that the comprehensive reutilization of copper zinc resource.
Such copper zinc vulcanizing mine stone is processed using the method for traditional ore dressing, because the natural floatability of sphalerite is fine, with
In Ore, the floatability of copper mineral is close, leads to copper-znic separation effect poor, and can not obtain qualified concentrate product.For example with
Conventional suppression zinc floats the technological process of copper, carries out copper and zinc bulk concentrate with " sodium sulfide+zinc sulfate+sodium sulfite " composite restrainer
FLOTATION SEPARATION is tested, and result shows, froth pulp cupric 15～20%, zinc 10～25%, and copper zinc flotation recovery rate is respectively 65
～70%, 60～65%；Product cupric 6～12%, zinc 4～8% in groove, copper zinc flotation recovery rate be respectively 10～15%, 5～
10%.As can be seen here, such copper zinc vulcanizing mine stone is processed using the method for traditional ore dressing, do not enable the effective of copper zinc mineral
Separate, also cannot get qualified concentrate product.
Above-described embodiment is only the preferable embodiment of the present invention, and the present invention can not enumerate out whole embodiment party
Formula, the technical scheme of all employing above-described embodiments, or the equivalent variations done according to above-described embodiment, all protect model in the present invention
In enclosing.
The content of book according to the above description, those skilled in the art in the invention can also be carried out to above-mentioned embodiment
Change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, some of the present invention are repaiied
Change and change in the scope of the claims that should also be as include the present invention.Although additionally, employing in this specification
Specific term, but these terms are merely for convenience of description, do not constitute any restriction to the present invention.Reality as above-mentioned in the present invention
Apply described in example, using same or other processes obtained from similar steps, all in the scope of the present invention.
Claims (7)
1. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore is it is characterised in that this technique is to vulcanize difficult copper zinc
Ore method for floating obtains copper and zinc bulk concentrate, and flotation concentrate directly carries out acidleach leaching, realizes copper-znic separation, is formed
The selecting smelting combination technique of " flotation-acidleach ".
2. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore according to claim 1 is it is characterised in that described copper
, mainly presented in chalcopyrite and secondary copper sulfide, about 60% zinc preservation is in sphalerite for copper in zinc vulcanizing mine stone
In, secondly it is zinc carbonate, a small amount of zinc sulfate, franklinite.
3. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore according to claim 1 is it is characterised in that described float
Choosing method is that copper zinc vulcanizing mine stone is carried out ore grinding, ore pulp that ore grinding obtains through " one roughing-coarse concentrate regrinding-triple cleaning-
Scan twice " flow process obtains copper and zinc bulk concentrate and mine tailing after sorting.
4. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore according to claim 1 is it is characterised in that described acid
Leaching leaching is that flotation copper and zinc bulk concentrate is placed in leaching tanks, adds concentrated sulphuric acid and is stirred leaching, is leached
Liquid, leachate carries out solid-liquid separation, and leached mud is high-quality copper concentrate, cupric>20%, contain zinc<5%, leachate lean solution follows
Ring using formed rich solution, more purified, concentrate, crystallisation by cooling operation, obtain sulphuric acid zinc product.
5. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore according to claim 3 is it is characterised in that ore grinding ore deposit
Slurry concentration is 75～82%；Mog -200 mesh > 65%；Flotation pulp concentration is 25～35%；The ph value of ore pulp for 8～
10.
6. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore according to claim 4 is it is characterised in that copper zinc mixes
Close concentrate by mass percentage its chemical composition be cu:15～20%, zn:8～25%, s: > 30%, remaining be gangue content and
Trace element.
7. a kind of selecting smelting combination technique processing difficultly-selected copper zinc Ore according to claim 4 is it is characterised in that acidleach temperature
Spend for 80～120 DEG C；Sulfuric acid concentration is 40～60%w/w；Sulphuric acid is 6:1～10:1 with the mass ratio of copper zinc concentrate；During leaching
Between be 2～3 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396154A (en) * | 2018-01-17 | 2018-08-14 | 昆明理工大学 | A method of recycling zinc-copper from zinc hydrometallurgy flotation of silver concentrate |
| CN111659530A (en) * | 2020-06-16 | 2020-09-15 | 昆明理工大学 | Method for dressing, smelting, recovering and separating continuous growth type copper-lead-zinc sulfide ore |
| CN112619904A (en) * | 2020-11-10 | 2021-04-09 | 西北矿冶研究院 | Method for reducing impurities in copper concentrate obtained by copper-zinc-iron separation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396154A (en) * | 2018-01-17 | 2018-08-14 | 昆明理工大学 | A method of recycling zinc-copper from zinc hydrometallurgy flotation of silver concentrate |
| CN111659530A (en) * | 2020-06-16 | 2020-09-15 | 昆明理工大学 | Method for dressing, smelting, recovering and separating continuous growth type copper-lead-zinc sulfide ore |
| CN111659530B (en) * | 2020-06-16 | 2021-03-23 | 昆明理工大学 | Method for dressing, smelting, recovering and separating continuous growth type copper-lead-zinc sulfide ore |
| CN112619904A (en) * | 2020-11-10 | 2021-04-09 | 西北矿冶研究院 | Method for reducing impurities in copper concentrate obtained by copper-zinc-iron separation |
| CN112619904B (en) * | 2020-11-10 | 2022-04-29 | 西北矿冶研究院 | Method for reducing impurities in copper concentrate obtained by copper-zinc-iron separation |
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