CN107674973A - A kind of method that mechanochemistry strengthens Leaching of chalcopyrite - Google Patents
A kind of method that mechanochemistry strengthens Leaching of chalcopyrite Download PDFInfo
- Publication number
- CN107674973A CN107674973A CN201711134430.2A CN201711134430A CN107674973A CN 107674973 A CN107674973 A CN 107674973A CN 201711134430 A CN201711134430 A CN 201711134430A CN 107674973 A CN107674973 A CN 107674973A
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- CN
- China
- Prior art keywords
- chalcopyrite
- leaching
- mechanochemistry
- strengthens
- oxidant
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Classifications
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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
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0082—Leaching or slurrying with water
-
- 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
-
- 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 kind of method that mechanochemistry strengthens Leaching of chalcopyrite, by chalcopyrite and oxidant in mass ratio 0~7:1 is mixed, and after planetary ball mill mechanical activation handles 0.25~3h, chalcopyrite and oxidant occur solid phase reaction and form new compound, then through pH is that 1~7 solution is leached at 40~85 DEG C, and copper is entered in solution in the form of copper ion during leaching.Compared with classical acid leaching method, the present invention has faster leaching rate, and copper leaching rate is up to 98%, therefore has vast application prospect.
Description
Technical field
The present invention relates to the technical field of hydrometallurgy, more particularly to a kind of mechanochemistry to strengthen the side of Leaching of chalcopyrite
Method.
Background technology
Tellurian copper has 70% to be present in chalcopyrite, as copper resource develops continuing to increase for dynamics, chalcopyrite money
Source mining grade constantly declines.Not only production cost is high for traditional pyrometallurgical smelting technical finesse low-grade chalcopyrite, and is calcined
During the gas that discharges can seriously pollute environment.Comparatively, wet type copper smelting technology has that cost is low, scale is big, resource is sharp
With degree height, good product quality, the construction period is short, environmental pollution is small the advantages that.However, traditional hydrometallurgical process chalcopyrite
Strengthen education means be mainly high temperature, high pressure, it is high leach agent concentration and strong mixing, its essence is the outside of Strengthen education reaction
Process, condition harshness but DeGrain, are primarily due to table in chalcopyrite lattice energy height, Stability Analysis of Structures, and leaching process
Face can form one or more layers passivation layer.
Currently, wet method leaching copper has Oxidation Leaching, coordination is leached and bioleaching process.Traditional sulfuric acid leaching is in temperature
It is calcined during 493~503K and chalcopyrite is changed into sulfate with acid effect, but the method produces the gas such as hydrogen sulfide, sulfur dioxide
Body, corrosion and severe exacerbation working environment are produced to equipment；Chloride leaching is that electricity occurs in the presence of iron chloride for chalcopyrite
Chemolysis, but the method produces acid, and severe corrosion equipment is, it is necessary to high performance anti-corrosion material Preparation equipment；Ammonia soaks under high pressure
When having oxygen, leached by stirring, but the method needs condition of high voltage, and also high is required to the seal of equipment；Bacterium
Leaching is to be widely used in Low Grade Copper Ore leaching, but leaching cycle is very long.Therefore, seek a kind of green, simple, effective
Strengthen education method is to improve the key of copper organic efficiency in chalcopyrite.
In recent years, with the development of mechanochemistry, mechanical activation is as a kind of emerging reinforcing means by more and more
Concern.Just there is researcher's discovery the twenties in last century, and mechanical energy is not necessarily all changed into heat in the grinding processes of crystalline solid
Can, the energy for having 5~10% is by solid sorbent, so as to increase in solid in the form of newly-generated surface and various defects
Can and reactivity, i.e., the activity of crystalline material is improved by mechanical force, thus mechanical activation receive domestic and international chemical industry and
The extensive concern of metallargist.So far, this respect has made remarkable progress, by bibliography (Jubasz Z.A method
for characterization of bulk structure and bulk stability of powders[J]
.Powder Technology,1985,42(2):123-129) understand, mechanochemistry is effect of the solid particle in mechanical energy
Under, because deformation, defect and dissociation etc. cause change of the material in structure, physicochemical properties and chemical reaction property etc.
Change.Mechanochemistry mainly produces mechanical activation in hydrometallurgy to mineral matter, so as to improve leaching process.The work of mechanical force
With physico-chemical properties such as the crystal structures for making mineral, there occurs the change of matter, interior energy substantially to increase, the equilibrium constant of Leach reaction and
Reaction rate significantly increases, and has very big invigoration effect to leaching of ores process, therefore is a kind of very effective mineral leaching
Go out reinforcing means, have the characteristics that simple to operate, flow is short, green, also achieving many in theoretical and application aspect has
The achievement of practical value, show good application prospect.
The content of the invention
Based on above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of mechanical enhancer brass
The method that ore deposit leaches.Chalcopyrite presses preset blending ratio batch mixing, after planetary mills machinery intensive treatment, chalcopyrite and oxidation with oxidant
Solid phase reaction generation metal salt occurs for agent, then through pH is the leaching of 1~7 solution, and copper is leached in the form of copper ion during leaching.
In order to solve the above-mentioned technical problem, the present invention provides a kind of method that mechanochemistry strengthens Leaching of chalcopyrite, comprising
Following steps：Chalcopyrite and oxidant batch mixing, after mechanical activation processing, then the aqueous solution through water or acid leaches.
As the preferred of above-mentioned technical proposal, the method that mechanochemistry provided by the invention strengthens Leaching of chalcopyrite is further
Including the part or all of of following technical characteristic：
As the improvement of above-mentioned technical proposal, the oxidant is ferric sulfate hydrate.
As the improvement of above-mentioned technical proposal, the particle diameter of the chalcopyrite is less than 2mm.
As the improvement of above-mentioned technical proposal, the oxidant is with chalcopyrite according to mass ratio 0~7:1 proportioning.
As the improvement of above-mentioned technical proposal, the mechanical activation process uses planetary ball mill, and planetary mills rotating speed is
300~700rpm, soak time are 0.25~3h.
As the improvement of above-mentioned technical proposal, the leaching process, used infusion solution pH is 1~7, extraction time
For 0.25h~3h, extraction temperature is 40~85 DEG C.
As the improvement of above-mentioned technical proposal, the acid is sulfuric acid.
Compared with prior art, technical scheme has the advantages that：
Mechanochemistry is combined by the present invention with wet-leaching, and chalcopyrite and oxidant generation solid phase are anti-after mechanical activation
Metal salt should be generated, so as to greatly speed up leaching velocity when leaching, copper leaching rate can reach 98% in 2h.
The present invention is activated at ambient pressure, and the temperature of leaching is at 40~85 DEG C, and technique is simple, environmental protection and economy, is had wide
Wealthy application prospect.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the present invention can
Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the accompanying drawing of embodiment will be simply situated between below
Continue.
Fig. 1 is the XRD spectrum of chalcopyrite in embodiment 1；
Fig. 2 is the XRD spectrum after chalcopyrite grinding in embodiment 1；
Fig. 3 is chalcopyrite in embodiment 2 and the XRD spectrum after ferric sulfate hydrate mixed grinding；
Fig. 4 is chalcopyrite in embodiment 3 and the XRD spectrum after ferric sulfate hydrate mixed grinding；
Fig. 5 is chalcopyrite in embodiment 4 and the XRD spectrum after ferric sulfate hydrate mixed grinding；
Fig. 6 (a) be activation 30mi n after sample figure；
Fig. 6 (b) be activation 120mi n after sample figure.
Embodiment
The following detailed description of the present invention embodiment, its as part of this specification, by embodiment come
Illustrate the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Embodiment 1
2g chalcopyrites (containing Cu 30.20%, S 31.59%, Fe 29.30%) are subjected to mechanical activation, planetary mills rotating speed
For 600rpm, milling time 2h.Compared to initial chalcopyrite (XRD spectrum is shown in Fig. 1), sample after grinding (XRD spectrum is shown in Fig. 2)
It is consistent with initial chalcopyrite diffraction peak-to-peak value, illustrate without the new material of generation, but diffraction maximum broadens, and relative intensity step-down, says
It is bright to destroy chalcopyrite perfection of crystal, make sample crystal grains fine.PH=1 sulfuric acid solution is configured, by the sample after grinding
Leached in water-bath, extraction temperature is 75 DEG C, extraction time 2h, and the leaching rate for measuring chalcopyrite in leachate is
8.25%.
Embodiment 2
By chalcopyrite and ferric sulfate hydrate (containing Fe 21%~23%) (gross weight 2g) example 1 in mass ratio:1 mixing is carried out
Mechanical activation, planetary mills rotating speed are 600rpm, milling time 2h, and its XRD spectrum is shown in Fig. 3.PH=1 sulfuric acid solution is configured,
Product after grinding is leached in water-bath, extraction temperature is 75 DEG C, extraction time 2h, measures chalcopyrite in leachate
Leaching rate be 39.32%.
Embodiment 3
By chalcopyrite and ferric sulfate hydrate (gross weight 2g) example 1 in mass ratio:4 mixing carry out mechanical activation, planet barreling
Mill speed is 600rpm, milling time 2h, and its XRD spectrum is shown in Fig. 4.PH=1 sulfuric acid solution is configured, by the product after grinding
Leached in water-bath, extraction temperature is 75 DEG C, extraction time 2h, and the leaching rate for measuring chalcopyrite in leachate is
85.74%.
Embodiment 4
By chalcopyrite and ferric sulfate hydrate (gross weight 2g) example 1 in mass ratio:7 mechanical activations, planetary mills grinding rate are
600rpm, milling time 2h, its XRD spectrum are shown in Fig. 5.PH=1 sulfuric acid solution is configured, by the product after grinding in water-bath
Inside leached, extraction temperature is 75 DEG C, extraction time 2h, and the leaching rate for measuring chalcopyrite in leachate is 97.51%.
Embodiment 5
By chalcopyrite and ferric sulfate hydrate (gross weight 2g) in mass ratio 1:7 mechanical activations, planetary mills grinding rate are
600rpm, milling time 2h.PH=7 solution is configured, the product after grinding is leached in water-bath, extraction temperature
For 75 DEG C, extraction time 2h, the leaching rate for measuring chalcopyrite in leachate is 97.44%.
By above example as can be seen that in the case of oxidant is not added, mechanical activation leaching of copper pyrites extracting rate is relatively low, with
The increase of oxidizer, caused salt is more after chalcopyrite after mechanical activation, and leaching rate gradually increases, final leaching rate
Reach 97.51%, illustrated that the addition of oxidant during mechanical activation promotes chalcopyrite reaction and generates sulfate.
Each raw material cited by the present invention, and bound, the section value of each raw material of the present invention, and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
Described above is the preferred embodiment of the present invention, can not limit the right model of the present invention with this certainly
Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, may be used also
To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.
Claims (8)
1. a kind of method that mechanochemistry strengthens Leaching of chalcopyrite, it is characterised in that comprise the following steps：Chalcopyrite and oxidant
Batch mixing, after mechanical activation processing, then the aqueous solution through water or acid leaches.
2. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The oxidant is water
Close ferric sulfate.
3. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The grain of the chalcopyrite
Footpath is less than 2mm.
4. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The oxidant and Huang
Copper mine is according to mass ratio 0~7:1 proportioning.
5. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The oxidant and Huang
Copper mine is according to mass ratio 1~7:1 proportioning.
6. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The mechanical activation mistake
Cheng Caiyong planetary ball mills, planetary mills rotating speed are 300~700rpm, and soak time is 0.25~3h.
7. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The leaching process,
Used infusion solution pH is 1~7, and extraction time is 0.25h~3h, and extraction temperature is 40~85 DEG C.
8. the method that mechanochemistry as claimed in claim 1 strengthens Leaching of chalcopyrite, it is characterised in that：The acid is sulfuric acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819818A (en) * | 2019-11-12 | 2020-02-21 | 长春黄金研究院有限公司 | Mechanical chemical pretreatment leaching gold extraction method for refractory gold ore |
| CN110819797A (en) * | 2019-11-21 | 2020-02-21 | 武汉理工大学 | Carbonate mineral leaching method |
| CN112680602A (en) * | 2020-12-18 | 2021-04-20 | 衢州华友钴新材料有限公司 | Treatment method for improving leaching efficiency of copper-containing sulfide ore |
| CN115000239A (en) * | 2022-05-11 | 2022-09-02 | 中南大学 | Method for preparing precursor solution of copper-zinc-tin-sulfur-selenium film solar cell by acid leaching of brass |
| CN115772606A (en) * | 2022-12-12 | 2023-03-10 | 昆明理工大学 | Method for leaching chalcopyrite by ultrasonically strengthening persulfate oxidation in hydrochloric acid system |
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| US5917116A (en) * | 1995-08-14 | 1999-06-29 | Dominion Mining Limited | Method for the processing of copper minerals |
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| CN104593608A (en) * | 2015-02-02 | 2015-05-06 | 上海第二工业大学 | Method for intensified leaching of rare earth metals from waste fluorescent powder by mechanical activation method |
| CN106011453A (en) * | 2016-05-31 | 2016-10-12 | 浙江三瑞铜业有限公司 | Method for treating cobalt-copper alloys |
| CN106755999A (en) * | 2016-12-21 | 2017-05-31 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5917116A (en) * | 1995-08-14 | 1999-06-29 | Dominion Mining Limited | Method for the processing of copper minerals |
| CN1249009A (en) * | 1997-03-03 | 2000-03-29 | 明特克公司 | Processf or the leaching of chalcopyrite |
| CN104593608A (en) * | 2015-02-02 | 2015-05-06 | 上海第二工业大学 | Method for intensified leaching of rare earth metals from waste fluorescent powder by mechanical activation method |
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| CN106755999A (en) * | 2016-12-21 | 2017-05-31 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819818A (en) * | 2019-11-12 | 2020-02-21 | 长春黄金研究院有限公司 | Mechanical chemical pretreatment leaching gold extraction method for refractory gold ore |
| CN110819797A (en) * | 2019-11-21 | 2020-02-21 | 武汉理工大学 | Carbonate mineral leaching method |
| CN112680602A (en) * | 2020-12-18 | 2021-04-20 | 衢州华友钴新材料有限公司 | Treatment method for improving leaching efficiency of copper-containing sulfide ore |
| CN115000239A (en) * | 2022-05-11 | 2022-09-02 | 中南大学 | Method for preparing precursor solution of copper-zinc-tin-sulfur-selenium film solar cell by acid leaching of brass |
| CN115000239B (en) * | 2022-05-11 | 2024-02-23 | 中南大学 | Method for preparing copper zinc tin sulfur selenium film solar cell precursor solution by acid leaching brass |
| CN115772606A (en) * | 2022-12-12 | 2023-03-10 | 昆明理工大学 | Method for leaching chalcopyrite by ultrasonically strengthening persulfate oxidation in hydrochloric acid system |
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