CN106345607B - A kind of selecting smelting combination technique handling difficultly-selected copper zinc ore - Google Patents
A kind of selecting smelting combination technique handling difficultly-selected copper zinc ore Download PDFInfo
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- CN106345607B CN106345607B CN201610768147.4A CN201610768147A CN106345607B CN 106345607 B CN106345607 B CN 106345607B CN 201610768147 A CN201610768147 A CN 201610768147A CN 106345607 B CN106345607 B CN 106345607B
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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
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Abstract
The invention discloses a kind of selecting smelting combination techniques for handling difficultly-selected copper zinc ore, the technique is that difficult copper zinc vulcanizing mine stone is obtained copper and zinc bulk concentrate with method for floating, flotation concentrate directly carries out acidleach leaching, realizes the separation of copper Zn-Ca series, forms the selecting smelting combination technique of " flotation-acidleach ".The invention has the advantages that the content of zinc in copper concentrate can be significantly reduced, to improve the grade of copper concentrate, and the comprehensive utilization of zinc in copper zinc vulcanizing mine stone is realized.Present invention process process is succinct efficiently, continuity is good, is easily achieved, rate of recovery height, is conducive to promote and apply in difficult copper zinc ore industrial production.
Description
Technical field
The present invention relates to the technique of preparing of sulphide ore in non-ferrous metal field, especially a kind of novel dressing and smelting united
Handle difficultly-selected copper zinc ore technology.
Background technique
Copper zinc vulcanizing mine stone is the important source material of copper smelting zinc, and fecund is in skarn type, hot-liquid type or hydrothermal filling and metasomatism
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, and needing fine grinding just can make them reach monomer dissociation, but crossing for fine grinding generation crushes
Phenomenon deteriorates floatation process, and the specific surface area of ore particle increases, while the soluble of copper mineral increases, and copper ion increases in ore pulp
More, zincblende becomes easily floating due to the activation by copper ion, 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 increasingly reduction for easily selecting copper-zinc ore resource, the ore that complicated difficultly-selected copper zinc polymetallic ore becomes important is provided
Source.The mineral disseminated grain size of certain Cu-Zn complex ores is thin, and some mutually contains in emulsion droplet shape；Copper mineral is many kinds of, and floatability is different；Contain
There are the more secondary pig copper and soluble heavy metal salt, activates zincblende, cause copper-znic separation ineffective.Traditional
Processing method is " protect copper lose zinc ", i.e., the output copper concentrate after ore dressing, and zinc is then used as impurity element to be present in copper concentrate,
Cause the very big wasting of resources.Copper concentrate sale when due to containing zinc it is higher need to make button live together reason, also further affect through
Ji benefit.As it can be seen that handling difficultly-selected copper zinc ore using traditional ore-dressing technique, copper-znic separation is difficult, metal recovery rate is lower.It is right
Similar difficultly-selected copper zinc ore carries out efficient, environmental protection and develop and uses, it has also become the important technological problems that ore dressing worker faces.
Therefore, it is necessary to develop a kind of new technique, such difficultly-selected copper zinc ore can be effectively treated, realize copper zinc resource
High efficiente callback utilize.
Summary of the invention
For difficulty existing for difficult copper-zinc ore assorting room, the present invention proposes a kind of novel dressing and smelting united
Difficultly-selected copper zinc ore technology is handled, for the technique on the basis of to the mixed choosing of copper zinc vulcanization raw ore progress copper zinc, use is hydrometallurgical
Method separates copper and zinc, the content of zinc metal in copper concentrate is on the one hand reduced, to improve the quality of copper concentrate, another party
Face avoids the waste of zinc resource, solves the comprehensive utilization of zinc resource.Selecting smelting combination technique tends to be simple making ore dressing process
While, metal recovery rate is substantially increased, copper zinc metal selects smelting overall recovery to increase, and preferably realizes
The resource comprehensive utilization of copper zinc mixing vulcanization raw ore utilizes.
Selecting smelting combination new process proposed by the present invention is achieved by the following technical solution.
A kind of selecting smelting combination new process handling difficultly-selected copper zinc ore obtains copper zinc mixing essence using the method for flotation first
Mine carries out acidleach leaching, realizes the separation of copper Zn-Ca series, 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 tailing.
Mainly there are in ore in the form of chalcopyrite and secondary copper sulfide for copper in the copper zinc vulcanizing mine stone
Zinc mineral is mainly zincblende.
The method for floating is that copper zinc vulcanizing mine stone is carried out ore grinding, and the ore pulp that ore grinding obtains passes through " one roughing-rough concentrate
Regrind-triple cleaning-scans twice " process obtains copper and zinc bulk concentrate and tailing after sorting.
Acidleach leaching is that flotation copper and zinc bulk concentrate is placed in leaching tanks, adds the concentrated sulfuric acid and is stirred leaching
Out, leachate is obtained, leachate is separated by solid-liquid separation, and leached mud is high-quality copper concentrate, and cupric>20% contains zinc<5%, leaching
Liquid lean solution recycles to form rich solution out, then purified, concentration, crystallisation by cooling process, obtains sulfuric 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 be 8~
10。
Its chemical component is Cu:15~20%, Zn:8~25%, S to above-mentioned copper and zinc bulk concentrate by mass percentage: >
30%, remaining is gangue content and microelement.
Leaching of the present invention is carried out in acid medium.In acid medium, zincblende surface occurs such as
Lower chemical reaction:
ZnS→Zn2++S+2e
Although the thermodynamical equilibrium current potential of oxidation reaction is lower, the poor ability of zincblende intrinsic conduction electronics.Therefore,
The dynamical resistance of oxidation is larger, oxidizing potential=thermodynamical equilibrium current potential+oxidation overpotential.This shows to dodge zinc under low potential
Mine surface does not have sulphur generation, and sulfide can just lose electronics and become elemental sulfur only under high potential.It is therefore possible to use
Concentrated acid and the method for heating improve the potential value of leaching medium, accelerate the oxidation of sulphur and the leaching of zinc in zincblende, to reach
The purpose of Selectively leaching zincblende.
Above-mentioned copper-znic separation process, at 80~120 DEG C, sulfuric acid concentration is 40~60% (mass ratioes), quality for temperature control
Than for 6:1~10:1, extraction time is in 2~3h.Leachate 5~30g/L containing zinc, zinc leaching rate can achieve 70% or more, and
Leachate cupric < 0.1g/L, copper leaching rate are lower than 1%.Above-mentioned leachate is separated by solid-liquid separation, leached mud is high-quality copper
Concentrate, leachate lean solution recycle to form rich solution, then purified, concentration, crystallisation by cooling process, obtain sulfuric acid zinc product, from
And realize the purpose of copper-znic separation.
Process flow provided by the invention is succinct efficiently, continuity is good, easily controllable, while can be improved time of copper, zinc
Yield is conducive to promote and apply in difficult copper zinc ore industrial production.
With reference to the accompanying drawings of the specification with the embodiment content that the present invention is further explained.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Copper zinc vulcanizing mine stone cupric 0.92%, zinc 0.81%, the lead 0.09%, sulphur 16.15%, silica of the present embodiment
36.86%, pick up from middle and lower reach of Yangtze River Large-scale Copper Mines.Copper sulfide mineral is mainly chalcopyrite in ore, be secondly class's copper mine,
Covellite and tetrahedrite add up to distributive law about 81.52%；Copper oxide mineral is mainly malachite, cuprite etc..Zinc ore in ore
Object is mainly zincblende, secondly distributive law about 59.26% is 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 relationship is complex.In particular, more package microfines and secondary micro- brilliant chalcopyrite in zincblende (<
5um), part copper zinc mineral output in the form of copper zinc mixture.
Copper zinc vulcanizing mine stone by Hubei Province formula spallar coarse crushing, fine crushing to roller spallar at fine ore, the control of fine ore granularity for-
20mm.Quantitative fine ore is weighed, pours into XMQ-240*90 type conical ball mill, clear water ore grinding is added to obtain initial ore pulp.Control
Ore grinding pulp density is 75~82%, -200 mesh of grinding fineness 65% or more.The initial ore pulp that ball mill is discharged is poured into XFD
Type single-trough flotating machine flotation, floatation concentration is 25~35%, the pH value of ore pulp is 8~10.Flotation with Z200 do collecting agent,
JT2000 does foaming agent, using in " one roughing-coarse concentrate regrinding-triple cleaning-is scanned twice " process flow flotation of ores
Copper-zinc sulphide minerals.Flotation concentrate is copper and zinc bulk concentrate, and flotation tailing, which enters, selects sulphur operation.Flotation concentrate cupric 15~
20%, zinc 8~25%, sulphur 25~35%, copper zinc flotation recovery rate are 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), mass ratio 6:1
Under conditions of~10:1, it is stirred leaching 2~3 hours.Leachate 5~30g/L containing zinc, zinc leaching rate can achieve 70% with
On, and leachate cupric < 0.1g/L, copper leaching rate are lower than 1%.Above-mentioned leachate is separated by solid-liquid separation, leached mud is height
Quality copper concentrate, cupric>20% contain zinc<5%.Leachate lean solution recycles to form rich solution, then purified, concentration, cooling knot
Brilliant process prepares sulfuric acid zinc product." flotation-acidleach " process integration provided by the invention, copper, zinc comprehensive recovery can distinguish
Up to 75~85%, 50~65%, the comprehensive reutilization of copper zinc resource is realized.
Such copper zinc vulcanizing mine stone is handled using the method for traditional ore dressing, since the natural floatability of zincblende is fine, with
The floatability of copper mineral is close in ore, causes copper-znic separation effect poor, and cannot obtain qualified concentrate product.For example, by using
Conventional suppression zinc floats the process flow of copper, carries out copper and zinc bulk concentrate with " vulcanized sodium+zinc sulfate+sodium sulfite " composite restrainer
FLOTATION SEPARATION experiment, the results showed that, froth pulp cupric 15~20%, zinc 10~25%, copper zinc flotation recovery rate is respectively 65
~70%, 60~65%；Product cupric 6~12%, zinc 4~8% in slot, copper zinc flotation recovery rate is respectively 10~15%, 5~
10%.It can be seen that handling such copper zinc vulcanizing mine stone using the method for traditional ore dressing, the effective of copper zinc mineral can not achieve
Separation also cannot get qualified concentrate product.
Above-described embodiment is only the preferable embodiment of the present invention, and the present invention cannot enumerate out whole embodiment party
Formula, all technical solutions using above-described embodiment, or the equivalent variations done according to above-described embodiment 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 carry out above embodiment
Change and modification.Therefore, the invention is not limited to the specific embodiments disclosed and described above, some repairs to of the invention
Changing and changing should also be as being included in scope of protection of the claims of the invention.In addition, although having been used in this specification some
Specific term, these terms are merely for convenience of description, does not limit the present invention in any way.Such as the above-mentioned reality of the present invention
It applies described in example, using other processes obtained from same or similar steps, all falls in the scope of protection of the present invention.
Claims (2)
1. a kind of selecting smelting combination technique for handling difficultly-selected copper zinc ore, which is characterized in that comprise the following steps that:
(1) ore dressing: choosing copper zinc vulcanizing mine, and copper sulfide mineral is mainly chalcopyrite in ore, is secondly class's copper mine, covellite and black
Copper mine adds up to distributive law about 81.52%, and the zinc mineral in ore is mainly zincblende, 60% zinc preservation in zincblende,
Secondary is zinc carbonate, a small amount of zinc sulfate, franklinite；
(2) muck: copper zinc vulcanizing mine stone is by Hubei Province formula spallar coarse crushing, fine crushing to roller spallar at fine ore, fine ore granularity control
For -20mm；
(3) ore grinding: weighing quantitative fine ore, pour into conical ball mill, and clear water ore grinding is added to obtain initial ore pulp, grinding fineness-
For 200 mesh 65% or more, ore grinding pulp density is 75~82%;
(4) flotation: pouring into single-trough flotating machine flotation for the initial ore pulp that ball mill is discharged, and flotation pulp concentration is 25~35%,
The pH value of ore pulp is 8~10；Flotation does collecting agent with Z200, JT2000 does foaming agent, using " one roughing-coarse concentrate regrinding-
Triple cleaning-is scanned twice " copper-zinc sulphide minerals in process flow flotation of ores；Flotation concentrate is copper and zinc bulk concentrate, is floated
Select tailing to enter and select sulphur operation, copper and zinc bulk concentrate by mass percentage its chemical component be Cu:15~20%, Zn:8~25%,
S: > 30%, remaining is gangue content and microelement；
(5) acidleach leaching: copper and zinc bulk concentrate is 80~120 DEG C in temperature, and sulfuric acid concentration is 40~60%, which is
Under conditions of the mass ratio of mass ratio, sulfuric acid and copper zinc concentrate is 6:1~10:1, it is stirred leaching 2~3 hours, leachate
Containing 5~30g/L of zinc, and leachate cupric < 0.1g/L；Wherein, in acid medium, it is anti-that following chemistry occurs for zincblende surface
It answers: ZnS → Zn2++S+2e；
(6) it is separated by solid-liquid separation: above-mentioned leachate being separated by solid-liquid separation, leached mud is high-quality copper concentrate, and cupric > 20% contains
Zinc < 5%；Leachate lean solution recycles to form rich solution；
Wherein, rich solution is purified again, is concentrated, crystallisation by cooling process, prepares sulfuric acid zinc product.
2. a kind of selecting smelting combination technique for handling difficultly-selected copper zinc ore according to claim 1, which is characterized in that copper zinc sulphur
Change the copper in ore mainly to exist in the form of chalcopyrite and secondary copper sulfide.
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| 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 |
| 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 |
| 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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| RU2135298C1 (en) * | 1998-03-06 | 1999-08-27 | Московский государственный институт стали и сплавов (технологический университет) | Copper-zinc concentrate separation process |
| CN101585017B (en) * | 2009-06-05 | 2013-04-03 | 湖南有色金属研究院 | Ore-selecting method of difficultly-selected copper zinc sulphur ore |
| CN101961673B (en) * | 2010-09-03 | 2014-03-26 | 罗光臣 | Combined concentration and smelting method for mixed copper ore |
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| CN103611624B (en) * | 2013-11-27 | 2015-11-25 | 中南大学 | A kind of flotation-acidleach process integration processing low-grade mixed copper ore |
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