CN1081239C - Processf or the leaching of chalcopyrite - Google Patents
Processf or the leaching of chalcopyrite Download PDFInfo
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- CN1081239C CN1081239C CN97182088A CN97182088A CN1081239C CN 1081239 C CN1081239 C CN 1081239C CN 97182088 A CN97182088 A CN 97182088A CN 97182088 A CN97182088 A CN 97182088A CN 1081239 C CN1081239 C CN 1081239C
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Abstract
The present invention provides a method for extracting copper from chalcopyrite by using iron sulfate, wherein the chalcopyrite is in a 'window' which is determined by experience within the width range of 350 to 450 mV by controlling the surface potential of the chalcopyrite to obtain qualified extracting rate. The most effective technological conditions comprise selection of the surface potential, extracting temperature, the pH value of an extracting solution, and the grinding fineness of the chalcopyrite. The present invention can be used for a tank extracting method and a heap extracting method.
Description
The leaching that the present invention relates to chalcopyrite is reclaiming copper wherein and to relate in particular to a kind of use preferably by bacteriogenic, but not necessarily, iron ion comes the method for the sulfide material in the oxidation chalcopyrite.
Use ferric sulfate sulfide oxidation mineral to leach sulfide and cause oxidation fast usually, and cause the dissolving of desired substance thus.In this case, the surface potential of mineral arrives in the scope of 660mV 550 usually, and leaching rate is considered to improve along with the increase of current potential usually.Such sulfide mineral is just like pyrite (FeS
2), arsenic-pyrite (FeAsS), copper glance (Cu
2S) and zink sulphide (ZnS).
Yet, for chalcopyrite, use ferric sulfate to leach the long time of cost, infer that this is the result of sulfide exposed surface passivation.The definite essence that passivation mechanism occurs is not exclusively clear and definite, and estimation is because formed passivation film at the chalcopyrite plane of crystal, thereby forms a diffusion impervious layer.
In order to overcome this difficulty, have been proposed in and attempt using activator or catalyzer in the leaching system.Show that silver is effective catalyzer (seeing as U.S. Patent No. 3856913).But, according to the knowledge of the applicant, there is not commercial run to use such catalyzer to operate, estimation is because silver-colored cost is high and its recovery is used for recirculation has difficulties.Also have other suggestion to use HgS, As
2S
3, SnS and CoS.Measure with regard to the applicant, can not prove that they are industrial effective.
Ahonen and Tuovinen be in " hydrometallurgy " (Hydrometallurgy) the 24th the 2nd phase of volume, 219-236 page or leaf, the katalysis of silver during the microorganism that discloses the ore materials that shakes the chalcopyrite that contains fine grinding in the bottle in 3 months nineteen nineties is leached.And US-A-4571387 has related to and uses the silver of sulfur bacteria and catalytic amount to leach copper from the ore of Containing Sulfur copper.
Therefore, the objective of the invention is, the effective ways that leach chalcopyrite are provided, and need use any expensive or deleterious activator or catalyzer.
According to the present invention, a kind of method that leaches chalcopyrite is provided, wherein use ferric sulfate to come the sulfide oxidation material.This method feature is, active CONTROL PROCESS condition, make the surface potential of chalcopyrite maintain in the scope of 350-450mV and continue at least one period working lipe, during this period of time leach, surface potential is measured with standard calomel electrode for referencial use.
Further feature of the present invention is to control iron ion (Fe at least by the oxygen supply of control ferrous ion oxidising process
3+) and ferrous ion (Fe
2+) ratio, thereby active CONTROL PROCESS condition, and use the bacterial oxidation method that ferrous ion is oxidized to iron ion, preferably independently carry out in the reaction vessel at one, the residence time of round-robin infusion solution can actively be controlled in the bacterial oxidation container like this.
Additional features of the present invention is, and is before leaching that chalcopyrite is levigate with the effective surface area that increases it with improve crystal dislocation, prevents the oxidation of The product sulfur element and at high temperature leach in leaching process.
Further feature of the present invention is, in successive loops, infusion solution is recycled to the iron ion regeneration step of bacterium, for infusion solution turns back to before leaching process gets ready, infusion solution is circulated to steps for copper removal such as solvent-extraction process or strike from leaching process, wherein removes dissolved copper to a certain extent.
When enforcement was of the present invention, it was important maintaining the surface potential of chalcopyrite in the specific narrow district.At this on the one hand, it is pointed out that because the sulfide grain of " in the corrosion " and the contact between the platinum electrode that the equilibrium potential of using platinum electrode and mercurous chloride electrode to measure is that the ore pulp redox potential is found and represents a blended current potential in the loop.For example the high electrochemical activity mineral are as the existence of the copper glance of following chalcopyrite, or the factors such as (battery effects) that contacts of low electrochemical activity mineral such as pyrite and chalcopyrite will strengthen real surface potential and use the difference of the pulp potential that platinum electrode measures.Comparatively ideal, should use the chalcopyrite crystalline electrodes or directly measure the surface potential of chalcopyrite by the composite electrode that chalcopyrite powder or enriched material are made.In addition, because the leaching kinetics of chalcopyrite is slow, the difference between ore pulp redox potential and the chalcopyrite surface potential always very little (being no more than 20mV).
Impurity in chalcopyrite also is considered to play the unstable that improves chalcopyrite and by its deliquescent catalyst action that causes.This effect and levigate be that sample is distinctive and depend on the source of sample to improve instable effect.This is to be produced by different earth physics conditions, forms the impurity that chalcopyrite also comprises different content therein under different earth physics conditions.
Method economic on the cost that uses on any particular ore or the enriched material is determined with following four basic variable experiences:
(i) surface potential of chalcopyrite;
The temperature that (ii) leaches;
The pH that (iii) leaches; With
The (iv) fineness that is ground to of ore or enriched material.
For above-mentioned aspect, have been found that scope or " window " difference of different its surface potentials of chalcopyrite, and clearly must depend on the mineralogical characteristic relevant with impurity of processed mineral with crystalline structure, crystal impurity and associated mineral.Similarly, most economical temperature, pH and mesh-of-grind also can be different.
The application of the inventive method can expand to and comprise that not only the drill traverse of utilizing stirring goes out the technology that method is handled the enriched material that contains chalcopyrite, also comprises and utilizes simple heap to spread out the technology that the diafiltration leaching method is handled the ore that contains chalcopyrite.
Control surface current potential or more generally, control ore pulp redox potential can realize with any mode easily in leaching process, this it will be apparent to those skilled in the art that, for example, supplies with the O of oxidising process by control
2And/or by changing the residence time in iron ion regenerative response independently.
In order to more fully understand the present invention, referring now to the different experiments of description of drawings enforcement.
In the drawings:
Fig. 1-the 3rd is illustrated in copper and zinc dissolving result in for some time and the figure of the ore pulp redox potential represented according to prior art on second y axle.
Fig. 4-the 6th, expression is according to the present invention copper dissolved figure from chalcopyrite under different leaching conditions.
Fig. 7 is the experimental installation loop diagram that uses in the indirect oxidation experiment of chalcopyrite.
Fig. 8 represents the leaching diagram result of different chalcopyrites.
Fig. 9 is the loop diagram of explanation pillar leaching experiment device.
Figure 10 and 11 is diagram results of two pillar leaching experiments.
Leaching experiment No.1 (Comparative Examples)
Batch biological experimental result that leaches that Fig. 1 represents to use South Africa copper-zinc sulphide flotation enriched material to carry out is not carried out for the surface potential of controlling chalcopyrite actively control process variable in experiment.Enriched material has 28% copper, 33% sulfide, 32% iron and 2% zinc by analysis.Copper almost without exception the form with chalcopyrite exists, and zinc then exists with the form of zink sulphide.
In a plastic channel that contains 2 liters of enriched material ore pulps, carry out biological leaching experiment.This groove has a circular cone base, is introduced at the bottom air of circular cone, is used for mixed ore pulp and biological reaction required oxygen and the carbonic acid gas of leaching is provided.Carbonic acid gas in the air supply replenishes with extra carbon dioxide, makes the whole volumetric concentration of carbonic acid gas be approximately 1000/1000000ths.Utilize the outside of infrared lamp heating of plastic groove, the temperature that biology is leached ore pulp is controlled at about 35 ℃.The starting point concentration of enriched material (quality-base) is 15%.The mesh-of-grind of enriched material is 80% by 75 μ m sieves.Leach medium and contain the required inorganic mineral salt nutrition of bacterial growth, wherein their concentration is, shows-ammonium sulfate 2, dipotassium hydrogen phosphate 0.5, sal epsom 0.5, nitrocalcite 0.05 with the gram numerical table in every liter of liquid.In the experiment beginning, add before the bacteria culture medium, add sulfuric acid initial pH value is adjusted to 1.8.The bacteria culture medium that uses is the mixed culture of iron-oxidizing bacterium, and it contains bacteriums such as thiobacillus ferrooxidant, thiobacillus thiooxidans and ferricoxidans.
The experimental result that Fig. 1 represents is typical to batch biological leaching experiment.One about 5 days lag phase was arranged when bacterial growth begins, then in ensuing 15 days, when bacterium ferrous ion (Fe
2+) iron that exists of form is oxidized to iron ion (Fe
3+) time, the ore pulp redox potential has one to increase rapidly, surpasses 600mV.During leaching, zinc is almost finished from the leaching that zink sulphide occurs together.Drop to 1.0 in experimental session pH value, this explanation sulfide is oxidized to sulfuric acid fully, analyzes the final residue that leaches and has confirmed this point.The graphic representation of Fig. 1 shows that for being commonly referred to be under the leaching condition of optimizing biological leaching sulfide mineral (high ore pulp redox potential), the leaching of copper from chalcopyrite only reached 5% after 34 days.When passivation appears in chalcopyrite, can be observed and leach kinetics and low copper extraction yield slowly.Leaching experiment No.2 (Comparative Examples)
Same South Africa chalcopyrite is carried out second batch of biological leaching experiment.In this embodiment, in a stainless steel tank that contains 10 liters of enriched material ore pulps, experimentize.Utilize a stirring motor up to drive one and have the stir shaft that is positioned near Lu Sidun (Ruston) turbine blade of trench bottom, mechanical stirring ore pulp.The air that is rich in and tests the carbonic acid gas of No.1 same concentrations is introduced in below the turbine blade just.Adopt the identical initial solids concn, mineral salt medium and the service temperature that provide among the experiment No.1 once more.Main not being both in this experiment, enriched material are ground to 90% degree of grinding by 20 μ m, and mensuration and pH value that do not allow ore pulp is reduced to below 2.0 with the grain size analysis instrument for this.This use to immerse the glass reference pH probe monitoring pH value of the combination in ore pulp and finishes, and its middle probe is connected with controller with meter, when pH drops to the adding that 2.0 controllers when following are controlled lime white.
Fig. 2 represents this experimental result.Leach through first 16 days copper and to reach about 20%, leaching rate surpasses the speed that obtains among the experiment No.1, thereby this gives the credit to the surface-area of the chalcopyrite that improves because of meticulous degree of grinding to a great extent.Leaching rate from the 17th day to 20 days copper shows a marked increase, to the extraction rate reached to 85% of the 21st day copper.
Dropping on 350mV with the ore pulp redox potential during leaching rate increases has directly to time period of this close limit of 400mV and gets in touch.The ore pulp redox potential rises to more than the 550mV fast after the 21st day, and the extraction of copper is ended under this condition.When experiment is finished to the analysis revealed of final leaching residue, the oxidation of sulfide has only appearred with regard to elementary sulfur.Leaching experiment No.3 (Comparative Examples)
Leaching condition is roughly identical with the condition of using in experiment No.2 in this Comparative Examples experiment.This experimental result is as shown in table 3.This experiment is with experiment the different of No.2, can be reduced to below 2.0 the 16th day pH value.This causes the generation of bacterial oxidation elementary sulfur, and shown in the data among Fig. 3, the speed that copper leaches reduces suddenly.This presentation of results element is thio-oxidizing to be played from the effect of chalcopyrite surface removal reaction component, and this has improved the unstable of chalcopyrite, and makes the chalcopyrite surface passivation occur subsequently.Leaching experiment No.4 (the present invention)
Use the sulfuric acid-ferric sulfate infusion solution of dilution to come the oxidation chalcopyrite, and the bioleaching process of the above-mentioned experiment No.3 of strict simulation carry out chemical leaching experiment.In the laboratory reaction container of 500 milliliters of capacity, carry out these experiments.These reaction vessels are furnished with temperature control, realize control by means of the double space layer in Glass Containers, and temperature required water is by this wall.Leach the magnetic couplings agitator mixing of ore pulp with container bottom.Utilize the combination glass-reference pH electrode in the container that the pH value of infusion solution is controlled at required level, this pH electrode links to each other with the automatic titrator that sulfuric acid is delivered in this container.Use the platinum and the reference electrode control ore pulp redox potential that are connected with automatic titrator in container, automatic titrator is delivered to proper amount of oxidant solution in this container.On the computer that volume is recorded in automatic titrator links to each other of oxygenant that in experiment, adds in time and acid.Being used for controlled oxidation reductive oxygenant is potassium permanganate solution.Selected Fe has been kept in the adding of this oxygenant
3+: Fe
2+Ratio, this ratio (by the Nernst equation) plays a major role to the redox potential of measuring.
The South Africa enriched material of the 13.8 gram fine grindings that use among the No.1-4 in experiment with have required pH value and 125 milliliters of infusion solutions of the concentration of iron of initial 3 grams per liters are incorporated in the container together, carry out leaching experiment.Initial infusion solution also contains the bacterium inorganic mineral salt nutrition of the given concentration of experiment No.1.Add permanganate solution and acid and carry out redox and pH control respectively in experimentation, ore pulp volume last in reaction vessel is usually about 400 milliliters.
With oxidation reduction potential control between 370-400mV, the pH value is 1.5 o'clock, experimentizes.Under 35,55,80 ℃ temperature, experimentize.In experimentation, can be from the amount of the oxygenant that adds with by analyzing in the end that enriched material leaches remaining copper the residue and definite final copper extraction yield calculates the copper amount of leaching.
Experimental result under 35 ℃ as shown in Figure 4.Show by observed data, leached through first copper of 1.5 days about 20%, after this leaching rate of copper improve so that after the 3rd day about 98% copper leached.Analyze final residue and show that sulfide is oxidized to elementary sulfur.Do not have bacterium to exist in these experiments, this shows that the pH value can reduce to below 2.0 and the oxidation of elementary sulfur and the reduction of chalcopyrite rate of oxidation do not take place.
Same data when Fig. 5 and 6 is illustrated respectively in 55 and 80 ℃, the leaching rate that these data declarations obtain raises along with temperature and improves.98% copper was extracted in 24 hours in the time of 55 ℃, and obtained 98% extraction yield in the time of 80 ℃ in 5 hours.Leaching experiment No.5 (the present invention)
This experiment is used to illustrate the operate continuously of using bacteriogenic iron ion to leach chalcopyrite, and the importance of explanation controlled oxidation reduction potential.For this reason, utilize the iron medium that in the indirect bacterial oxidation system of an operate continuously, produces, carry out the leaching of chalcopyrite.The indirect oxidation experimental loop of adopting as shown in Figure 7.
Sulfide oxidation reactor (1) has 10 liters working volume, and it turns round as one-level continuously stirred tank reactor (CSTR) (CSTR).This reactor is by mechanical stirring but there is not air to introduce.Will with experiment among the No1-4 employed identical chalcopyrite as the flow of slurry continuous-feeding of 10% solid phase in reactor.Liquid phase contains as the described dissolved bacterium of above-mentioned experiment inorganic mineral salt nutrition in this stream.The selection of the volume feed rate of feed ore pulp is relevant with required solid retention time.With the volumetric rate identical, remove and leach residual ore pulp simultaneously with the speed of feed ore pulp.Sulfuric acid is joined in the oxide sulfate reactor, be used to control the pH value.
The required iron ion of leaching in sulfide oxidation reactor reaction one independently the iron ion of bacterium produce generation in the step (2).In order to promote this step, from the sulfide oxidation reactor, remove continuously and contain by leaching the dissolved Fe that reaction produces
2+Ore pulp, be transported to simple taper settling vessel (3) then and carry out the solid-liquid separating step.
Precipitated solid turns back in the sulfide oxidation reactor, and liquid is transported to (4) in the holding tank.Liquid is transported to the electrolyzer (5) from this holding tank, to remove copper from solution, becomes metallic copper.Do like this is to maintain in the required scope for the concentration with dissolved copper in the loop.This infusion solution is transported in the bacterium iron ion maker (2), to finish Fe then
2+To Fe
3+Reoxidize.
The maker (2) that uses comprises 15 liters of column form objects, and this column form object comprises the netted thing of the stainless steel of vertical placement, is used for fixation of bacteria groove passively.The bacterial cultures that uses is identical with the mixed culture that has illustrated.With the air that is rich in carbonic acid gas, in the bottom enough to guarantee from Fe
2+To Fe
3+The unrestricted flow of bacterial oxidation, be sprayed into grow up to be a useful person (2).The temperature of maker is controlled in about 35 ℃.
Usually under the redox potential of＞600mV, regeneration liquid is transported to second storage tanks (6) from reactor.Locating every now and then in (7), a part of ferric iron of second storage tanks of artificial removal precipitates to reduce the total concn of the iron in the loop.The liquid of removing iron turns back to second storage tanks.
Then, the liquid of high redox potential is transferred and gets back in the sulfide oxidation reactor.In the sulfide oxidation reactor, by the high Fe of high redox potential
3+The adding rate-controlling redox potential of liquid, and be used in reactor that controller is connected in platinum and reference electrode monitoring, controller is connected with pump (8), pump (8) is connected with second storage tanks (6).Use with reactor that controller is connected in the glass-reference pH electrode of combination, be controlled at the pH value in the sulfide oxidation reactor, wherein this controller is controlled the sulfuric acid amount that is distributed in the reactor.
Indirectly successfully operate continuously two months of bacterial oxidation system.Respectively by precipitated iron and electrolytic copper, between the total concn of iron and copper is controlled in all the time and restrains for every liter 15 and 25.In the sulfide oxidation reactor, the residence time of chalcopyrite maintains 24 hours.Temperature in the sulfide oxidation reactor maintains 55 ℃ all the time.
The surface potential of chalcopyrite 380mV, at this moment corresponding the measurement ore pulp redox potential when being controlled at 390mV in the sulfide oxidation groove has set up first stable state operational condition.The degree that leaches copper and zinc from the feed solid is respectively 74% and 94%.Measurable 72% bronze medal leaching that obtains is very identical with testing that the mathematical model that the pure chemistry of enriched material leaches data and one-level CSTR 55 ℃ time the shown in the No.4 (Fig. 5) combine for this.
Second stable state is based upon under the same experiment condition, but the ore pulp redox potential of controlling in the sulfide oxidation reactor is high slightly, is 400mV.The leaching degree of copper drops to 45% under this higher current potential, and this has illustrated the susceptibility for the selected current potential of any specific chalcopyrite.On the contrary, what can reckon with is, sulfide mineral is under higher redox potential, and the leaching degree of zinc is increased to more than 94%.Leaching experiment No.6
With with experiment No.4 described similar mode, utilize dilute sulphuric acid-ferric sulfate oxidation to carry out a series of chemical leaching experiment, use North America cupric sulfide enriched material to carry out leaching experiment.Enriched material is 30.3% bronze medal, 34.3% sulfide and 29.9% iron by analysis.Wherein copper almost without exception have (enriched material quality 77%) with the chalcopyrite form, only contain the sulfide (copper glance, alpha chalcocite, covellite) of a spot of (about 2% quality) other copper.Other sulfide that significantly exist are pyrite (7% quality).The initial degree of grinding of enriched material sample is 90% by 103.8 μ m.
Under 35 ℃ temperature, carry out first group of two chemical leaching experiment.The ore pulp oxidation reduction potential control is carried out these two experiments when 394mV and 444mV.Under same redox potential, carry out two experiments of second group, be ground to 90% enriched material by 6.9 μ m but be to use.This experimental results reduction is in table 1.
Table 1 is in the time of 35 ℃, and the iron of North America chalcopyrite enriched material leaches
| The grinding of enriched material (90% is no more than) | Ore pulp redox potential (mV is to SCE) | Dissolved copper (%) after 48 hours |
| 103.8 | 394 | 10.5 |
| 103.8 | 444 | 16.1 |
| 6.9 | 394 | 16.8 |
| 6.9 | 444 | 15.9 |
The chalcopyrite enriched material of fine grinding can pass through to increase the surface-area that leaches or improve the crystallization dislocation usually, thereby improves the extraction yield of leaching kinetics and copper.To this enriched material, the meticulousr grinding of enriched material does not improve the extraction yield that leaches kinetics and copper.The copper extraction yield that obtains under two kinds of redox potentials that adopt is no more than 17%.
For this more resistant to elevated temperatures chalcopyrite enriched material, satisfied copper leaches kinetics and extraction yield is necessary to obtaining usually in the raising of extraction temperature.
Use original enriched material and fine grinding to the 90% enriched material sample by 6.9 μ m to carry out further serial experiment at 70 ℃.To each enriched material sample, the ore pulp redox potential be 394,404,414,424,434 and 444mV under carry out six experiments.Experimental results reduction is in Fig. 8.
For the enriched material of fine grinding (90% by 6.9 μ m), experimental result shows, 414 in the redox potential scope of 434mV in 48 hours, can reach high copper recovery (＞98%).This more than potential range or following leaching kinetics to copper all unfavorable.But this experimental result shows that also (90% by 103.9 μ m) also may obtain high relatively copper extraction yield for thicker original enriched material, but in should be about the 414mV narrower scope of its redox potential.Conclusion is, for this enriched material, by adopting the redox potential in the scope of the 414mV left and right sides, can avoid the fine grinding enriched material to improve that copper leaches kinetics and the rate of recovery and the tooling cost that increases.Ore pillar leaching experiment
Use the indirect biological heap leaching method of pillar leaching experiment simulation of ore particles, wherein,, generate dilute sulphuric acid-ferric sulfate infusion solution the diafiltration ore storage in the outside of ore storage at one independently in the ferric iron production process of bacterium.A critical aspects of this indirect bioleaching process is that the redox potential of this infusion solution (ratio of iron and ferrous ion) can be selected.Itself and direct biological heap leaching are contrasted,, comprise that oxidation of divalent becomes the bacterial oxidation of ferric iron to react the inside that occurs in ore storage, and if if possible, the controlled oxidation reduction potential is extremely difficult for direct biological heap leaching.
The experimental installation that uses in the pillar leaching experiment of laboratory is shown in the wiring diagram of Fig. 9.In the plastic column of 0.12 meter of high 1 meter, diameter, use the rock sample of the pulverizing of about 15Kg to carry out the pillar leaching experiment.Post (9) have one around jacket pipe (10), make the temperature in the post be controlled at 35 ℃.Described liquid carries out diafiltration with the speed of 27 liters of every square metre of mineral surface per hour by column form object, and is collected in the storage tank (11) of column bottom.By adding superoxol in storage tank, required iron that will be in storage tank: ferrous ratio (redox potential) is controlled at required level.This has simulated the ferric iron regeneration step of outside bacterium effectively.Make nitrogen bubble enter in the storage tank liquid and mix promoting, also from the bottom by the ore post to reduce the chance that the ore particles of bacterium post grown.
Leach liquor contain with leaching experiment No.1 in the bacteriotrophy thing of same concentrations.The pH value of the leach liquor in storage tank is controlled in 0.8 by adding sulfuric acid.
The mineral sample is 1.07% bronze medal, 3.5% iron and 2.1% sulfide by analysis.Mineralogical analysis shows that the mass content of the sulfide mineral of ore approximately is 1.5% chalcopyrite, 0.5% copper glance, alpha chalcocite and covellite,＜0.5% purple copper and 2.5% pyrite.For the amount of further evaluation non-chalcopyrite cupric sulfide and chalcopyrite in ore, a sample of ore is carried out prussiate leach.Have been found that common non-chalcopyrite cupric sulfide to be soluble in prussiate and chalcopyrite is difficult for molten.This leaching is the result show, 51% copper exists with the non-chalcopyrite cupric sulfide of easy leaching, and the 49% remaining form with chalcopyrite exists.Pillar leaching experiment 1
Use is crushed to-and the ore of 6mm carries out two contrast experiments.In an experiment, the redox potential of storage tank is controlled in " high oxidation reduction " level of 505mV, is controlled at " suboxide reduction " level of 396mV in another experiment.These the results are shown among Figure 10, have wherein described the copper recovery percent estimated according to copper in the solution relation corresponding to extraction time.These data obtain high copper extraction yield when showing beginning, estimation is that final extraction yield reaches balance when 67% the highest bronze medal extraction yield because easily the non-chalcopyrite cupric sulfide that leaches leaches under high redox potential soon.The leaching rate of copper is low under the suboxide reduction potential, and estimation is because non-chalcopyrite cupric sulfide leaching rate under the suboxide reduction potential is low, but final copper extraction yield reaches balance at higher value 83% place.Suppose that in each case all copper that easily leach are reasonably by leaching, and get 49% copper and exist, can calculate 33% under high redox potential, being leached of copper of chalcopyrite form with the chalcopyrite form.Under the suboxide reduction potential, the chalcopyrite that can calculate leaching similarly is increased to 65%.Pillar leaching experiment 2
This leaching experiment is similar to pillar leaching experiment 1 in many aspects.Rock sample is crushed to-12mm in this embodiment, and carries out this leaching experiment in two stages-starting stage in 135 days, wherein uses high redox potential (505mV) and subordinate phase, wherein redox potential is adjusted to low-level (396mV).This experimental result is shown in Figure 11.
When the starting stage had high redox potential, the extraction yield of copper finally reached balance at 58% maximum value place after 135 days.Suppose that once more all non-chalcopyrites leach, the copper that can calculate 14% chalcopyrite is in this case leached.After the redox potential of the 135th day leach liquor reduces, the leaching of the copper that amount is outer, extraction yield finally reaches balance at 81% place.What can calculate once more is the copper extraction yield of the chalcopyrite of this expression total 61%.
Conclusion is got up, and above-mentioned experimental data shows that under high redox potential, the extraction yield of copper is low from the chalcopyrite component of ore, because chalcopyrite passivation under these conditions, this situation is observed usually.Even in more complicated ore diafiltration leaching method, under suboxide reduction potential scope, leach, the leaching of chalcopyrite also can improve, and the extra factor such as the precipitation of filtration efficiency, mass transport effect and iron and sulphur may be main processing parameters in described method.
Be understandable that from above, the invention provides simple method and be used for leaching copper from chalcopyrite effectively that do not use any expensive or other deleterious catalyzer or activators and do not relate to, it relies on control fully and parameter and the condition of leaching is set.
Be understandable that other embodiments that do not break away from the scope of the invention are feasible.
Claims (8)
1. a method that leaches chalcopyrite wherein under the condition that does not have silver catalyst, is used ferric sulfate sulfide oxidation material, the method is characterized in that, by being controlled at the iron ion (Fe in the infusion solution
3+) and ferrous ion (Fe
2+) ratio the surface potential of chalcopyrite is maintained in the scope of the 350-450mV that measures as reference electrode with the standard calomel.
2. according to the process of claim 1 wherein that the process that ferrous ion is oxidized to iron ion is the process of a bacterial oxidation.
3. according to the method for claim 2, wherein control the ratio of iron ion and ferrous ion to the oxygen-supplying amount of bacterial oxidation step by control.
4. according to any one method in claim 2 or 3, wherein independently carrying out described bacterial oxidation process in the reactor, and infusion solution is being circulated in leaching process.
5. according to the method for claim 4, can be the described bacterial oxidation process of carrying out under the required redox potential of 350-450mV wherein exceeding the scope that leaches infusion solution in the reactor, and join the adding speed that leaches in the reactor by controlling rich ferric infusion solution, control the redox potential that leaches in the reactor.
6. according to the method for claim 5, wherein extra processing condition are selected from:
(i) at surface potential scope between 350 to 450mV or the real surface current potential between 350 to 450mV;
The (ii) temperature of extract technology;
The (iii) pH value of extract technology; With
The (iv) mesh-of-grind of chalcopyrite
They are rule of thumb selected to improve the efficient of this technology.
7. according to the method for claim 6, wherein infusion solution is recycled to the step of removing copper from extract technology, to remove a part of dissolved copper.
8. according to the method for claim 4, wherein this method is a kind of heap leaching method, wherein uses infusion solution so that described surface potential to be provided.
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| AUPR855201A0 (en) * | 2001-10-29 | 2001-11-29 | Technological Resources Pty Limited | Recovery of copper from chalcopyrite |
| CN1320137C (en) * | 2002-12-31 | 2007-06-06 | 熊尚彬 | Compound leaching agent and leaching method for leaching out copper pyrite using compound leaching agent |
| AU2005207973B2 (en) * | 2004-01-30 | 2009-07-16 | Consolidated Nominees (Pty) Ltd | Heap bioleaching process |
| CN101857916B (en) * | 2010-05-24 | 2012-05-09 | 北京科技大学 | Liquid distributing method in tank leaching process |
| US10023935B2 (en) | 2014-09-12 | 2018-07-17 | Flsmidth A/S | System and method for enhanced metal recovery during atmospheric leaching of metal sulfides |
| WO2016081799A1 (en) * | 2014-11-20 | 2016-05-26 | Flsmidth A/S | System and method for enhanced metal recovery during atmospheric leaching of metal sulfides |
| CN105039693B (en) * | 2015-08-05 | 2017-09-22 | 中南大学 | A kind of bioleaching process for strengthening chalcopyrite and bornite |
| US20190382869A1 (en) * | 2015-10-30 | 2019-12-19 | Technological Resources Pty. Limited | Heap Leaching |
| CN106755999B (en) * | 2016-12-21 | 2018-11-23 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
| CN107164633A (en) * | 2017-04-07 | 2017-09-15 | 中南大学 | A kind of method of high-efficiency comprehensive utilization argentiferous refractory brick |
| CN107674973B (en) * | 2017-11-16 | 2019-08-06 | 武汉理工大学 | A kind of method that mechanochemistry strengthens Leaching of chalcopyrite |
| CN112221695B (en) * | 2020-09-28 | 2022-09-30 | 穆索诺伊矿业简易股份有限公司 | Copper separation and smelting combined copper extraction method for copper oxide ores with different oxidation rates |
| CN112522511B (en) * | 2020-11-09 | 2021-12-10 | 紫金矿业集团股份有限公司 | Waste rock recycling method for refuse dump |
| CN114381599B (en) * | 2021-12-28 | 2023-03-14 | 北京科技大学 | Method for synergistically strengthening sulfuric acid leaching of chalcopyrite |
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|---|---|---|---|---|
| US3856913A (en) * | 1972-09-21 | 1974-12-24 | British Columbia Res Council | Copper extraction by rapid bacteriological process |
| US4571387A (en) * | 1983-01-26 | 1986-02-18 | British Columbia Research Council | Biological-acid leach process |
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- 1997-03-03 CN CN97182088A patent/CN1081239C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856913A (en) * | 1972-09-21 | 1974-12-24 | British Columbia Res Council | Copper extraction by rapid bacteriological process |
| US4571387A (en) * | 1983-01-26 | 1986-02-18 | British Columbia Research Council | Biological-acid leach process |
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