CN1732277A - Recovering metals from sulfidic materials - Google Patents
Recovering metals from sulfidic materials Download PDFInfo
- Publication number
- CN1732277A CN1732277A CNA2003801080516A CN200380108051A CN1732277A CN 1732277 A CN1732277 A CN 1732277A CN A2003801080516 A CNA2003801080516 A CN A2003801080516A CN 200380108051 A CN200380108051 A CN 200380108051A CN 1732277 A CN1732277 A CN 1732277A
- Authority
- CN
- China
- Prior art keywords
- solution
- oxidation
- stage
- raw material
- leaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims description 70
- 239000002184 metal Substances 0.000 title claims description 70
- 150000002739 metals Chemical class 0.000 title claims description 5
- 239000000243 solution Substances 0.000 claims abstract description 290
- 238000000034 method Methods 0.000 claims abstract description 245
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 198
- 230000003647 oxidation Effects 0.000 claims abstract description 185
- 239000010970 precious metal Substances 0.000 claims abstract description 109
- 230000008569 process Effects 0.000 claims abstract description 79
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 150000004820 halides Chemical class 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims description 176
- 229910052785 arsenic Inorganic materials 0.000 claims description 151
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 133
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 132
- 239000012535 impurity Substances 0.000 claims description 123
- 239000010931 gold Substances 0.000 claims description 97
- 229910052683 pyrite Inorganic materials 0.000 claims description 95
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 94
- 239000011028 pyrite Substances 0.000 claims description 94
- 229910052737 gold Inorganic materials 0.000 claims description 92
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 90
- 239000002994 raw material Substances 0.000 claims description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- 229910052964 arsenopyrite Inorganic materials 0.000 claims description 75
- 229910052799 carbon Inorganic materials 0.000 claims description 75
- 239000007787 solid Substances 0.000 claims description 75
- 239000010949 copper Substances 0.000 claims description 73
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 claims description 70
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- 238000001556 precipitation Methods 0.000 claims description 54
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- 238000011084 recovery Methods 0.000 claims description 48
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- 238000001354 calcination Methods 0.000 claims description 31
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- 230000001590 oxidative effect Effects 0.000 claims description 23
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 21
- 238000011109 contamination Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
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- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 9
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- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
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- 238000004458 analytical method Methods 0.000 description 20
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- 235000012970 cakes Nutrition 0.000 description 16
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- 239000000706 filtrate Substances 0.000 description 13
- 239000005864 Sulphur Substances 0.000 description 12
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- 229910052569 sulfide mineral Inorganic materials 0.000 description 12
- 229910052787 antimony Inorganic materials 0.000 description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 11
- 239000012267 brine Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
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- 238000005303 weighing Methods 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
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- 208000003556 Dry Eye Syndromes Diseases 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
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- 230000008901 benefit Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
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- -1 platinum metals Chemical class 0.000 description 6
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
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- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 3
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- 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
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Abstract
A process for recovering a precious metal from a sulfidic material comprises the steps of preparing an acidic aqueous halide solution having an oxidation potential sufficient to oxidise the sulfidic material and render the precious metal soluble in the solution, adding the material to the acidic aqueous halide solution so that the sulfidic material is oxidised and the precious metal is solubilised and separating the precious metal from the oxidised sulfidic material. In addition, a process for removing a contaminant from a contaminated sulfidic material comprises the steps of mixing the material in an aqueous solution wherein a multi-valent species of a relatively high oxidation state oxidises the contaminant to render it soluble in the solution, produces a contaminant refined material, and is reduced to a relatively lower oxidation state; and removing the contaminant from the solution whilst regenerating the multi-valent species to its relatively high oxidation state.
Description
Technical field
The present invention relates to a kind of method that from sulfidic materials, reclaims metal, particularly reclaim for example method of gold of precious metal.Present method can be applicable to sulfidic materials uncontaminated and that pollute, comprises containing higher carbon content (so-called " dual infusibility raw material ") or not having or those sulfidic materials of low carbon content (so-called " single infusibility raw material ").The word of Shi Yonging " higher carbon content " is meant that carbon content in the sulfidic materials generally is higher than the carbon content of about 2 weight % here.
Background technology
A large amount of settlings and a large amount of sulfidic materials are all arranged all over the world, and the metal, particularly precious metal that the hope that containing in them has economic worth is reclaimed be gold and silver-colored for example.For example, there are a large amount of settlings and a large amount of pyrite to comprise gold and/or silver and other precious metal for example platinum and platinum metals.
The reluctant impurity of in these settlings some is arsenic, antimony, bismuth or other heavy metal contaminants for example.When having high-content carbon, because carbon and for example golden complexing of precious metal, they have high avidity, the complexity so the processing of mineral also can become.
The method of the sulfide oxidation of present commercial employing comprises calcining, pressure oxidation (POx) and bio-oxidation (Biox).In pressure oxidation and bio-oxidation process, generally use sulfate medium.
Because the calcining sulfide mineral can discharge the deleterious sulfurous gas of environment (so-called SO
xGas), so there is significant problem in this method.When in the mineral substance arsenic being arranged, produce for example ARSENIC TRI OXIDE 98 of deleterious material.Owing to these reasons, international trend is a method of abandoning the calcining sulfide minerals.
The method of use pressure oxidation sulfidic materials can avoid calcining the problem of generation, but this needs high pressure (generally being higher than 30 crust) and relative higher temperature (being higher than 200 ℃).And pressure oxidation is generally carried out in containing the solution of vitriol.
US6461577 discloses a kind of bio-oxidation process of handling arsenical sulfidic materials, and wherein the sulfidic materials experience is carried out two sections bio-oxidations processing with dissolving arsenic.The structure of leaching process is complicated, because it uses the biological bacterium of leaching.In addition, disadvantageously, bio-oxidation is slow.
US4053305 discloses a kind of leaching method that uses solution of ferrous chloride and pressurised oxygen to reclaim copper and silver from sulfide minerals.Although copper dissolution in leach liquor, does not allow silver leach intentionally, silver and solid residue pass through leach liquor together.Must use environmentally harmful leaching agent sodium cyanide from this resistates, to extract silver.
The oxygen that US4410496 discloses a kind of solution that uses calcium chloride or bariumchloride and pressurization reclaims the leaching method of copper, lead and zinc from sulfide minerals.And the precious metal in the mineral substance does not still leach, and they and solid residue pass through leach liquor together, thereby must extract individually.
US4655829 discloses a kind of leaching method that reclaims metal from the sulfide minerals that comprises arsenic and antimony.In the method, prepare block sulfide concentrate (concentrate) from the red arsenic mineral substance.In excessive calcium chloride solution with this concentrate furnishing slurry.In case be prepared into concentrate, just need to measure the total metal contents in soil and the composition of this concentrate.In method, in order to prevent to produce soluble arsenic compound or deleterious arsenic steam, this concentrate and the balanced solution slurry that comprises copper, lead, zinc or their mixture of the sulphided form of predetermined concentration are mixed.In this, collective concentrate and balanced solution slurry form the reaction slurry with predetermined metal content, make the volumetric molar concentration of arsenic and antimony in the mixture approximate the volumetric molar concentration of copper, lead and zinc, in about 60～40 or 40～60 scope.Have only this mixture of balance rightly, it just can be heated and inflate under pressure, is soluble component with these burnings.In other words, balance is necessary, makes not produce solubility arsenic compound or deleterious arsenic steam.
If provide a simple Wet-process metallurgy method to reclaim particularly gold of precious metal from sulfidic materials, that will be useful.
Summary of the invention
First aspect the invention provides a kind of method that reclaims precious metal from sulfidic materials, and the method comprising the steps of:
Prepare a kind of acid halide aqueous solution, this solution has sufficient oxidizing potential with the oxidation of sulfureted raw material and make precious metal dissolve in this solution;
Sulfidic materials is added in this acid halide aqueous solution, makes sulfidic materials oxidation and make precious metal dissolving; With
Separate precious metal from the sulfidic materials of oxidation.
The inventor finds amazedly, when keeping sufficient oxidizing potential in the acidic halide solution, in an independent stage, can make the precious metal dissolving when sulfidic materials is oxidized.
And the contriver is surprised to find, and when sulfidic materials was polluted by arsenic, antimony etc., in an independent stage, in the precious metal dissolving, arsenic etc. were leached simultaneously and precipitate, and do not need solution equilibria step prior or beginning.
So, aspect second in, the invention provides a kind of method that from the sulfidic materials that pollutes, reclaims precious metal, the method comprising the steps of:
Prepare a kind of acid halide aqueous solution, this solution has sufficient oxidizing potential with the oxidation of sulfureted raw material and make precious metal dissolve in this solution, and this solution has the sedimentary pH value of the arsenic of making;
Sulfidic materials is added in this acid halide aqueous solution, makes the sulfidic materials oxidation, the precious metal dissolving, and make the arsenic precipitation; With
Separate precious metal from the sulfidic materials of oxidation and sedimentary arsenic.
The method of first and second aspects also is different from pressure oxidation and bio-oxidation process, and difference is that preceding method uses the infusion solution based on halogenide rather than vitriol.
The contriver has been noted that for example gold formation strong complex of halogenide (as prussiate) and precious metal, thereby can promote the dissolving of precious metal, and can promote to adopt subsequently for example recovery of the precious metal of carbon absorption.But because halogenide is than the part a little less than the prussiate, so the contriver developed a kind of method, and wherein, the precious metal that reaches similar prussiate with abundant high oxidizing potential (Eh) in sour environment (preferred pH＜3) dissolves ability.
Advantageously, this method can be with the operation of closed loop or Recycle design, the economic advantages of following with generation (for example simple, less energy-consumption, observe conservation of matter etc.).The contriver also observes, and can use this method and reclaim precious metal from any sulfidic materials, and described sulfidic materials comprises infusible mineral substance and concentrate, for example has the dual infusibility raw material (for example carbonaceous arsenopyrite) of higher carbon content.
Preferably, in solids-liquid separation step containing the solution of precious metal and oxidized sulfidic materials and sedimentary arsenic (if there is) separated, reclaim precious metal in the metal recovery stage from this solution then, recovery is general preferred to be undertaken by being adsorbed onto on the gac in one or more carbonaceous posts.Preferably after precious metal is adsorbed onto on the gac, carbon burning is removed to reclaim precious metal, perhaps use the cyanide solution elution, make eluant then, reclaim precious metal with the electrolysis process for extracting through electrolysis stage.At this on the one hand, present method advantageously is different from existing business method, and the resistates that needs the cyaniding oxidation in the conventional method is to extract precious metal (gold), and this needs independent special leach circuit.In the present invention, therefore precious metal dissolving when leaching does not need to leach with prussiate.In addition, present many environment departments require to destroy remaining prussiate, and particularly in the zone of environment sensitive, this has increased fringe cost.
In untainted sulfidic materials (for example not by the single infusibility pyrite of pollutions such as arsenic), generally in a stage, carry out the oxidation of sulfidic materials.In the sulfidic materials that pollutes (for example single or dual infusibility pyrite that is polluted by arsenic and/or carbon etc.), although can reach the precious metal dissolving in the fs in two stages, the oxidation of sulfidic materials is generally carried out in two stages.
After stage, generally it is recycled to the sulfidic materials oxidation stage through metal recovery at solution.Preferably after solids-liquid separation step and in solution circulated, provide to tandem a metal recovery stage before the sulfidic materials oxidation stage.A stage (that is, " loop " is by forming to returning the sulfidic materials oxidation stage from solution circulated) that provides as the part of solution circulation loop is provided employed term " tandem ".In addition, can use the outer metal recovery processes of de-carbon absorption, comprising ion-exchange, solvent extraction etc.
In the situation of the carbonaceous dual refractory mineral matter of bag, need to be equipped with in addition an independent metal recovery stage (promptly being separated to solution circulation loop), to reclaim from sulfidic materials oxidation stage and the raw material solid precious metal of process together.Because some precious metal (for example gold) and carbon do not have dissolving by oxidising process together, so need this separation phase.This independent metal recovery stage can be used common calcining or melting method, and selectively use to leach after the calcining (for example using solution), remain in precious metal (for example gold) in the burnt solid material with recovery from the sulfidic materials oxidation stage.
Usually, the precious metal that reclaim is a gold, but also can be silver, platinum or other platinum metals, reclaims these metals and can prove that generally this method has economy.
Most preferably, described halide solution is the soluble metal halide solution, and general halide concentration is about 8 mol.Preferred described halogenide is muriate, but also can be bromide or halid mixture such as muriate and bromide for example.
This method of preferred operations makes the solution metal of dissolved metal halide play the multivalence species.In this respect, the selection of multivalence species generally is that it had both had the higher state of oxidation to participate in the oxidation of sulfidic materials, had the lower state of oxidation that is reverted to when oxidation again.Advantageously, renewable subsequently these multivalence species are to its higher state of oxidation, and after this these regenerated multivalence species can be recycled to the sulfidic materials oxidation stage, to participate in further oxidation.Advantageously, carry out the regeneration of multivalence species in the leaching stage, make the regenerated species can loop back the sulfidic materials oxidation stage,, produce the advantage (for example observing conservation of matter, simple, less energy-consumption etc.) of economic aspect thereupon as the preferred closed loop of present method or the part of Recycle design.
Usually, the metal in the metal halide solution is a copper, but also can be iron etc.Any of these multivalence species can both serve as electron transfer agent effectively.For example, in the solution that is recycled to the sulfidic materials oxidation step, metal is in the higher state of oxidation (for example Cu (II) or Fe (III)), and it is in the lower state of oxidation (for example Cu (I) or Fe (II)) after the oxidation.In the leaching stage, generally there be (be high with the low state of oxidation) in the multivalence species with ion pair.But, can use other multivalence species, wherein can comprise cobalt, manganese and vanadium.
When sulfidic materials was arsenopyrite, by the controlled oxidation current potential, arsenic can leach in the solution in the first leaching stage.But, preferably control the pH value of solution value and make arsenic leaching in a single day just precipitate with ferric arsenate (scorodite).And when sulfidic materials is arsenopyrite, preferably leach the pyrite component, and also controlling the pH value of solution value, to keep arsenic be the ferric arsenate throw out in the second leaching stage.Like this, arsenic is just separated from this method together in solids-liquid separation step and solid residue, does not disturb precious metal to reclaim.
For untainted single infusibility pyrite raw material, the sulfidic materials oxidation stage generally comprises a single leaching stage, wherein pyrite raw material oxidation, precious metal dissolving simultaneously.
Can also flow or operate upstream each leaching stage, in this, each stage can comprise one or more containers.
Preferably will be supplied to for the second leaching stage from first complete soln that leaches the stage.
When sulfidic materials during for example by arsenic contamination, generally in the first leaching stage, this raw material contacts with the solution that is in the Eh that can enough leach impurity and dissolving precious metal (for example gold), and preferably Eh is about 0.7～0.8 volt (reference electrode is standard hydrogen electrode (SHE)).Under the Eh of this solution, the pyrite component of raw material does not leach basically.Preferably in the first leaching stage pH of solution less than 1, but greater than about 0.5, so that precipitation immediately after making impurity leach.Preferably solution temperature is about 80～105 ℃ in the first leaching stage, more typically is 80～95 ℃.
For untainted sulfidic materials (using single leaching during the stage) or for the employed second leaching stage of pyrite component of leaching in the sulfidic materials that pollutes, usually raw material and have can enough leach pyritous Eh, preferably the solution of about 0.8～0.9 volt Eh contacts.And usually the pH value of solution is less than 1, but greater than about 0.2, so that precipitate immediately after making impurity leach.Equally, for pyritous leaching, solution temperature is general identical with the arsenopyrite leaching or be higher than the leaching of arsenopyrite, generally is about 90～105 ℃.
In order in single or the second leaching stage, to obtain higher solution E h, need to add other oxygenant for example oxygen, air, chlorine, hydrogen peroxide etc.For the pH value of solution that is optimized is precipitation forms and reclaimed copper ion to keep impurity, need in single or the second leaching stage, add acid for example sulfuric acid and/or alkali for example lime carbonate is promoting pH, otherwise arsenic and iron will not precipitate, but dissolve.In this, no matter be the single leaching stage or the second leaching stage, the oxidation of the pyrite component of raw material can produce sufficient or excessive sulfuric acid.Alternatively, can use the hydrochloric acid that do not disturb this process reaction or other acid.
Yet, leaching the isolated solution in back and be sent to the precious metal recovery stage, isolated residual solid generally is sent to the disposal stage.
Preferably after precious metal reclaims, use the solution adjusting stage to remove (precipitation) ferric sulfate, control the content of these species in this process thus.Usually in this solution, add Wingdale and lime carbonate to form rhombohedral iron ore/gypsum precipitate, filter then and together discard with solid residue from the stage of leaching in this stage.But preferably the adding by regulating Wingdale is controlled removing of iron thus to keep iron certain in the solution; prevent cupric precipitation again (promptly conversely; because iron precipitates under lower pH than copper, buffer pH value during its precipitation, thereby the copper precipitation is shielded).
Preferably from solution, filter out solid residue, but also can use for example solid-liquid sedimentation of other separation method, solution evaporation, centrifugation etc. in solids-liquid separation step.
When having high-load carbon (for example carbon of 2～20 weight %) in the sulfidic materials, can be advantageously when the sulfidic materials oxidation with tensio-active agent for example sequestering agent join in the solution to prevent that precious metal (for example gold) is adsorbed onto on the carbon in the raw material.Described sequestering agent generally is one or more organic solvents, comprises kerosene, phenolic ether etc.Alternatively, activated carbon can be joined preferentially adsorbed gold in the solution.The independent metal recovery stage of using sequestering agent or gac can need not to be used for separating any precious metal, and the carbon in these precious metals and the solid residue flows away together.
The best application of present method is about reclaiming precious metal from pyrite and concentrate, and wherein, impurity generally is arsenic, antimony, bismuth, mercury, cadmium etc. and is present in those metals in many known pyrite raw materials natively.
The tangible metal of other economic benefit be can reclaim extraly in the method, copper, nickel, zinc, lead etc. comprised.In addition, in specific application, impurity itself is worth maybe needing to reclaim.For example, impurity is valuable economically or environment is deleterious, this make and it need be reclaimed from the contamination precipitation thing (for example, for impurity for example antimony, bismuth, calcium etc. that's how things stand).
When sulfidic materials is polluted by arsenic, antimony etc., use the method for second aspect.In this method, in the single stage, the precious metal dissolving, impurity leaches and precipitation simultaneously, does not need prior or initial solution equilibria step.In some applications, for example to reclaim (for example being worth) individually when impurity, or during as just the replacement of the method for second aspect, be worth contamination precipitation and impurity leaching are separated because it has certain economic.
Therefore, aspect the 3rd in, the invention provides a kind of method of from the sulfidic materials that pollutes, removing impurity, the method comprising the steps of:
Described raw material is blended in the aqueous solution, wherein, the multivalence species oxidation impurities of the higher state of oxidation, so that impurity dissolves in this solution and produce the raw material of having removed impurity, and these multivalence species are reduced the lower state of oxidation; With
From solution, remove impurity, simultaneously these multivalence species are regenerated to the higher state of oxidation.
This method can advantageously reclaim again pollution the complexing of sulfidic materials institute metal, particularly precious metal for example the gold.In addition, remove decon in the time of by regeneration multivalence species, can advantageously operate this method with closed loop or recycle scheme, the subsidiary advantage that produces economic aspect is for example simple, less energy-consumption, observe conservation of matter etc.
At some in other the application,, also need impurity leached and separate with contamination precipitation for example when when another that needs to remove impurity or the method aspect second before the common calcining of sulfide minerals or the melting replaced.
Therefore, in fourth aspect, the invention provides a kind of method of removing impurity from the sulfidic materials that pollutes, the method comprising the steps of:
Described raw material is blended in the aqueous solution, and the oxidizing potential of this solution only is controlled as basically oxidation impurities so that impurity dissolves in this solution, thereby produces the raw material of having removed impurity; With
This solution is separated with the raw material of having removed impurity.
By the controlled oxidation current potential, the method for the 4th aspect can advantageously make impurity maintain soluble form, makes its follow-up removing (for example in independent settling step) become easy like this.
For example, when described raw material is arsenopyrite and impurity when being arsenic, for example leach stage controlled oxidation current potential and make arsenic oxidation and dissolving, and pyrite is not oxidized first.In addition, in the method for the 3rd and fourth aspect, in case arsenic dissolved with separates, the pyrite composition that is left can be oxidized more tempestuously in follow-up (for example second) the leaching stage.
Phrase " has been removed the raw material of impurity " and has been comprised such raw material, wherein, fully therefrom do not remove impurity, but have enough low impurity level, make it can be further processed (for example in calcining furnace and smelting furnace), or satisfy environmental standard of allowing of waste etc. etc.The general method of third and fourth aspect of using is handled pyrite or concentrate, and impurity wherein generally comprises arsenic, antimony, bismuth, mercury and cadmium.These impurity are present in many known pyrite raw materials natively.The method of third and fourth aspect also can be applied to reluctant mineral substance and concentrate, for example the dual refractory mineral matter of arsenopyrite, particularly high-carbon content.
In the method aspect third and fourth, generally, from solution, remove impurity through precipitation at independent precipitate phase by oxygenant is incorporated in the solution.Advantageously, oxygenant can make the multivalence species be oxidized to the higher state of oxidation simultaneously.In precipitation with remove impurity and the multivalence species are regenerated after high oxidation state more, can make solution circulated arrive the leaching stage then.
At precipitate phase, pH value of solution generally maintains about 1.5～3.Generally keep pH value of solution by regulating to solution supply oxygenant and/or alkaline reagents.When needs add alkaline reagents, generally add basic salt for example lime carbonate, calcium oxide, yellow soda ash, sodium bicarbonate etc.
In precipitate phase, oxygenant generally precipitates oxidation of impurities (for example with arsenic from+3 being oxidized to+5 oxidation state) to more not diffluent form, simultaneous oxidation the multivalence species.Described oxygenant can be air, oxygen, chlorine, hydrogen peroxide etc.In pyrite, impurity is generally with the form of iron/oxide impurity precipitate (for example being ferric arsenate when impurity is arsenic).
After contamination precipitation, generally solution E h and pH are returned to impurity and leach needed level, so that can make solution circulated arrive the leaching stage.For example after contamination precipitation, can reach this purpose by the adding of regulating oxygenant.
In the method aspect third and fourth, impurity is can be in single or multistage leaching process oxidized and leach in the solution.Usually leaching process comprises the first leaching stage and the second leaching stage, in the first leaching stage, the controlled oxidation current potential basically only oxidation impurities so that impurity dissolves in this solution, in the second leaching stage, improve oxidizing potential with oxidation removal the sulfide in the raw material of impurity.In this, preferably leach stage oxidation and a large amount of impurity of dissolving, and can leach the remaining impurity of stage oxidation second first.
And each leaching stage can and be flowed ground or operation upstream, and in this respect, each stage can comprise one or more containers.
Removed the raw material of impurity and generally after the first leaching stage, from solution, separated, and be supplied to for the second leaching stage.In addition, by the precipitation in the precipitate phase, generally after each leaching stage, solution is separated with the raw material of having removed impurity, usually so that therefrom remove impurity.
In the method aspect third and fourth, when sulfidic materials is pyrite raw material (for example pyrite of arsenopyrite or other pollution), in the first leaching stage, impurity generally under the highest about 105 ℃ temperature and pH less than 1 acidic aqueous solution in oxidation, the Eh of solution enough with oxidation of impurities in solution, but do not leach pyrite substantially, Eh generally is about 0.7～0.8 volt (reference electrode is a standard hydrogen electrode).In the second leaching stage, the pyrite raw material also under the highest about 105 ℃ temperature and pH less than 1 acidic aqueous solution in oxidation, but the higher pyritous solution E h of enough leachings, Eh generally is about 0.8～0.9 volt.In order to obtain higher solution E h, can in solution, add oxygenant for example oxygen, air, chlorine, hydrogen peroxide etc. in the second leaching stage.And as required, can add for example sulfuric acid of acid.
In the second leaching stage, for the low pH value of solution of keeping oxidation of pyrite and the remaining arsenic that generally exists with+5 oxidation state of dissolving, for example sulfuric acid, hydrochloric acid or other do not disturb the acid of this process reaction to need to add acid to it yet.But, also can not add acid when in solution, producing enough sulfuric acid (for example the sulphur that ought be present in mineral substance or the concentrate is oxidized, thereby).
Method as first and second aspects, round-robin solution generally is the dissolved solution of metal chloride in whole leaching and precipitate phase, the chloride concentration of this solution is about 8 mol, and the metal in the dissolved solution of metal chloride plays multivalence species (defined in the method as first and second aspects).
Method as first and second aspects, when having high-load carbon (for example carbon of 2～20 weight %) in the sulfidic materials, can be advantageously in oxidation of impurities (leaching) step with tensio-active agent for example sequestering agent join in the solution, be adsorbed onto on the carbon in the raw material to prevent dissolved metal (particularly precious metal for example gold).Use sequestering agent can need not carbon to be separated with precious metal by calcining.
So, aspect the 5th, the invention provides the sulfide of pollution that a kind of processing has higher carbon content to reclaim the method for the precious metal in the raw material, the method comprising the steps of:
-in the aqueous solution, leach described raw material, wherein, described metal leaches in the described solution, and the carbon of sheltering simultaneously in the raw material is adsorbed on the carbon to prevent precious metal; With
-from solution, reclaim precious metal.
Phrase " higher carbon content " is meant that the carbon that exists generally is about the level of 2～20 weight % in described sulfidic materials.
Shelter carbon with sequestering agent as defined above.The method of the 5th aspect is defined identical aspect others and first to fourth.
In precipitation with remove impurity and the multivalence species are regenerated after higher oxidation state, solution generally is recycled to the leaching stage.Because the multivalence species were reproduced originally the oxidation state of (before leaching), so it can participate in further oxidation and leaching.
In the method aspect third and fourth, can provide the metal recovery stage to leach in the solution together and/or the metal that in the remaining raw material of removing impurity, exists with recovery and impurity.
For example in the situation of the dual refractory mineral matter that contains carbon, after the last leaching stage, need a metal recovery stage, be recovered in exist in the remaining raw material of removing impurity for example be adsorbed onto metal (for example, precious metal such as gold etc.) on the carbon.And in the situation of dual refractory mineral matter, because impurity is removed from sulfidic materials basically when leaching, so the metal recovery stage can comprise common calcining or fusion process.Optionally, after calcining, can use chlorine or prussiate to leach, to reclaim residual metallic in the burnt solid material (for example, when this metal be that precious metal is for example during gold).
Alternatively or additionally, in (promptly between oxidation of impurities and precipitation) before the contamination precipitation or afterwards (promptly at contamination precipitation and be recycled between the oxidation stage) can need a tandem metal recovery stage, leaches into solution metal to remove in the leaching stage.Term " tandem " is meant a stage that is arranged in solution circulation loop.The general tandem metal recovery stage comprises solution metal is adsorbed onto on the carbon in the carbon post, and this carbon generally is gac.Alternatively, other metal recovery processes be can use, ion-exchange, solvent extraction etc. comprised.
The typical metal that reclaims in the method aspect third and fourth comprises precious metal for example gold and silver, platinum or other platinum metals, reclaims the economy that these metals generally can prove this method.But, can be alternatively or reclaim the significant metal of other economy extraly, comprise copper, nickel, zinc, lead etc.In addition, the specific of the method aspect third and fourth should be on the way, and impurity itself is worth maybe needing to reclaim.For example, impurity has economic worth to get or is harmful to environment, and this impels it is reclaimed (for example, this is that impurity is the situation of antimony, bismuth, cadmium etc.) from the contamination precipitation thing.When impurity is exactly when needing " metal " of recovery, an impurity recovery stage to be set extraly or alternatively after contamination precipitation.
Before the metal recovery in the method aspect third and fourth, generally provide many raw material separation phases from solution, to separate the raw material of having removed impurity.About this point, generally after the first leaching stage, solution is delivered to enriching stage concentrate, and from solution, separate the raw material of having removed impurity.Generally after the second leaching stage, from solution, filter out the raw material of having removed impurity, but can use for example solid-liquid sedimentation of other separation method, solution evaporation, centrifugation etc.
Like this, isolated solution generally carries out the impurity recovery after every section of the first and second leaching stages, and isolated refining raw material need carry out metal recovery (for example in the pyritous situation of dual infusibility) or discard.
In addition, in the method aspect third and fourth, after the stage, generally provide an impurity separation phase, so that from solution, remove impurity before solution circulated being returned the leaching stage (or before tandem metal recovery stage) at contamination precipitation.About this point, the general use solid/liquid separation stage after contamination precipitation, this solid/liquid separation can use filtration or other separation method to carry out.
Description of drawings
Drop on scheme in the scope of the invention although have other, only be explained with reference to the drawings preferred version of the present invention now in the mode of embodiment, wherein:
Fig. 1 contrasts the preferred method (IRGP) that reclaims precious metal from sulfidic materials of the present invention, has schematically described the representative of the generalized approach of the pressure oxidation of prior art and bio-oxidation process;
Fig. 2 has described schematically that (arsenopyrite-FeAsS) reclaims the generalized method flow diagram of first kind of scheme of precious metal (gold) from the sulfidic materials that pollutes;
Fig. 3 and 4 has described extract and the solution E h and the time relation of IRGP gold and iron in each stage;
Fig. 5 has schematically described the generalized approach schema of second kind of scheme, the figure shows from sulfidic materials to remove impurity and reclaim precious metal from sulfidic materials;
Fig. 6 has schematically described to remove impurity and reclaim the method flow diagram of the preferred method of precious metal from sulfidic materials from single infusibility sulfidic materials;
Fig. 7 has schematically described to remove impurity and reclaim the method flow diagram of the preferred method of precious metal from sulfidic materials from dual infusibility sulfidic materials;
Fig. 8 is (arsenic) infusion solution parameter of various fs (reaction times) figure of changing in time of the method for depiction 6 and 7; With
Fig. 9 is various subordinate phase (pyrite) infusion solution parameter (reaction times) figure of changing in time of the method for depiction 6 and 7.
Embodiment
Before the mode with embodiment describes the preferred method of the present invention in detail, at first the preferred method of the present invention is briefly described with reference to Fig. 1 and in conjunction with existing pressure oxidation and bio-oxidation process.
In this detailed description the preferred method of the present invention be called English Tyke infusibility gold method (IntecRefractory Gold Process, IRGP).These methods of being developed be from infusible sulfide mineral sediment, reclaim gold based on halid alternatives.These sedimental known treatment methods generally are that the flotation fine ore is produced concentrate, then handle sulfide minerals mainly is oxidized to vitriol, use prussiate to extract gold at last from oxidation residues.
The commercial selection scheme of sulfide oxidation mineral substance comprises calcining, pressure oxidation and bio-oxidation at present.Compare with present hydrometallurgy operation (pressure oxidation and bio-oxidation), the associated viscera of IRGP schematically is depicted among Fig. 1.IRGP advantageously is different from the pressure oxidation of hydrometallurgy and the place of bio-oxidation scheme is, IRGP uses halogenide rather than sulfate medium.Gold is insoluble to vitriol, and halogenation image prussiate is the same and goldenly form strong complex compound, thus promote its dissolving and subsequently pass through to be adsorbed onto the recovery of carrying out on the gac.Because halogenide is than the part a little less than the prussiate, use sour environment (pH＜2) to obtain identical golden extraction efficiency with current potential (Eh) with higher solution temperature.
For the processing of infusibility sulfide, the halogenide medium that is in controlled solution oxide current potential makes arsenic and sulfide oxidation and gold dissolving.After auriferous solution is separated from the sulfide mineral slurry of oxidation, can reclaim the dissolved gold on the gac by being adsorbed onto, calcine gac then, or use the prussiate elution, so that finally reclaim metallic gold by electrowinning.IRGP does not resemble present business-like operation, and IRGP does not need to make the oxidation residues cyaniding when gold extracts, and cyaniding needs independent special leach circuit, and may need the one-tenth of both expensive to destroy remaining prussiate originally.
Cause auriferous mineral infusible factor to have many, as shown in the table:
| Type | The reason of refractory properties |
| Separate out | Be locked in silicate, sulfide, the carbon etc. with physics mode |
| Shelter | Because of forming the chemical layer passivation |
| Reaction | Form gold-containing compound for example gold telluride and the inferior gold of antimonyization |
| Exchange | Gold in the mineral lattice (for example " sosoloid " gold in the pyrite mineral) is replaced by element |
| Absorption | The carbon material of " activity " absorption dissolved gold in the mineral slurry |
The exploitation of IRGP is specifically designed to the concentrate that processing is produced by those refractory minerals that drop in back two classes " exchange " and " absorption ".The major part of world gold storage capacity drops in this two class, and they mainly are the sulfide for example arsenopyrite and the pyrite of iron, and arsenopyrite and pyrite or Individual existence perhaps more generally mix and exist.When " activity " carbon also existed in the mineral, IRGP also was suitable for.
IRGP method and the chemical reaction of handling the infusibility gold ore that comprises following mineral type described now.
1. arsenopyrite
2. arsenopyrite+pyrite
3. arsenopyrite+pyrite+carbon
The chemical reaction of arsenopyrite oxidation
The existence of arsenic in the infusibility gold ore mainly is the form with arsenopyrite (FeAsS).Usually gold is " locked " in this arsenopyrite mainly as the species that fettered by lattice, usually is called sosoloid, rather than proof gold.Therefore gold is separated out and is needed completely destroy arsenopyrite lattice.
Realize the destruction of arsenopyrite lattice among the IRGP according to the chemical oxidation of following total reaction.
Because the solubleness of oxygen in this treatment solution is very low, thus not direct oxidation of oxygen arsenopyrite, but work by several intermediate steps.
By the direct supply oxygen of air, be ejected in the leach liquor with normal atmosphere, originally adopt oxygen to produce cupric ion (Cu according to following reaction
2+) the solubilized oxygenant of form:
This reaction occurs on the interface between air filled cavity and the treatment solution.Cupric ion is according to following reaction oxidation pyrite then:
Further then injected air is according to reaction (2) and following reaction, and ferrous and cuprous reaction product is oxidized:
When ferric ion exists, form insoluble ferric arsenate easily according to following reaction arsenic acid:
Can form ferric arsenate in perchloride electrolytic solution, under the employed operational condition of IRGP, ferric arsenate generally is a crystal in this environment, and is stable, and this makes it easily to be separated.
Because the iron of a small amount of background concentration always is present in the treatment solution, so Cu
2+/ Cu
+The effect of ion pair is by Fe
3+/ Fe
2+The ion pair compensation.When oxygen exists, at Cu
2+And Fe
3+Influence available current potential down is in the zone of 850mV (with respect to SHE).Make golden stabilization owing to forming chloride complex according to following reaction, so this current potential is enough for the dissolving of gold:
In treatment solution, exist bromine when (for example, adding), also can form gold-bromo-complex according to following reaction if having a mind to:
Containing the Cu of 20～40g/L
2+The Fe of ion and 2～5g/L
3+In the ionic 8M chloride electrolyte, under 90～95 ℃ temperature, carry out oxidation.
The chemical reaction of oxidation of pyrite
Pyritous oxidation is carried out according to following total reaction among the IRGP, wherein Jing Li a series of intermediate reactions and arsenopyrite oxidation experienced identical:
Notice that pyritous sulphur is until being oxidized to vitriol, by contrast, the sulphur of arsenopyrite only is oxidized to the sulphur of element state.
Therefore pyrite use thinner particle to obtain the acceptable response kinetics of explained later than arsenopyrite infusibility more.But one samples of pyrite shows the reactivity of variation, it is believed that this is the influence that replaced by arsenic by a part of sulphur in the lattice.Such pyrite usually is called as arsenopyrite, and arsenic impurities content is high more, and the pyrite reactivity is 1 true arsenopyrite more near the As/S ratio.
In the employed same liquid of arsenopyrite oxidation, under 90～95 ℃ temperature, by Cu as arsenopyrite
2+/ Cu
+Ion pair is reacted according to following reaction:
According to reaction (2) and (4), Cu
+And Fe
2+Injected again dioxygen oxidation.Adding Wingdale under about 1～1.5 pH, is rhombohedral iron ore and gypsum with the ferric sulfate that forms according to following reaction precipitation:
The adding of control Wingdale is to keep soluble iron ion in the scope of 2～5g/L, and this prevents from the cupric precipitation and be lost to leach in the resistates.
Concentrate grinds size
The concentrate that is used for IRGP generally 80% less than 70～100 microns magnitude range in.Test shows that when concentrate was ground to thinner size (depending on the characteristic of each indivedual concentrate) again, reaction kinetics obviously improved, and in first kind of processing scheme (describing below), generally used regrind.At arsenopyrite is only during auriferous mineral, and 80% can fully obtain good gold less than 30～40 microns size proof extracts and acceptable leaching retention time.
When gold is enclosed in the pyrite, grind size and depend on pyritous reactivity substantially, as described above, changes of reactivity is bigger.For highly active pyrite, use the employed grinding of arsenopyrite, but more the infusible samples of pyrite needs thinner grinding.Sometimes extend to extra-fine grinding, 80% less than 6～10 microns in more unusual infusible situation.The contriver also notices, in the past 10 years, the level of extra-fine grinding technology has developed at global mining site many super grinders that all successfully turning round.
The recovery of gold
Auriferous infusion solution is through containing the post of activated carbon, and gold is adsorbed onto on this post.The retention time of gold absorption is 10～15 minutes, is similar to the routine work of prussiate system.Because (be generally 10～100mg/L), the gold that loads on the carbon is generally 2～5 weight % to gold concentration higher in the solution, and this is the result of typical high gold content concentrate.Destroy carbon by burning in stove and reclaim the gold of such load.When hanging down load, be more economical with prussiate elution and then activated carbon.
Impurity is handled
Except main impurity (for example arsenic, antimony etc.), the existence of impurity in the raw material concentrate (for example Cd, Mn, Mg etc.) does not produce injurious effects to leaching and precipitation operation.But adopt the method for handling impurity to prevent their accumulations in time in treatment soln.This can precipitate by the relief liquor that makes regeneration cupric solution with the purifying salt solution that turns back to this process realizes.Importantly IRGP does not produce any waste liquid, and all impurity are all removed as solid by-product.
Wingdale joined in this relief liquor to regulate pH be 3.5, iron and copper that precipitation is remaining remove by filter precipitation, and relief liquor loops back leach liquor.Form insoluble oxide compound for 9 times to remove impurity for example Cd, Mn, Mg by adding white lime at pH, filtered and recycled precipitates and it is discarded.
Aspect treatment facility, the similar part of IRGP and bio-oxidation process is that IRGP uses normal atmosphere, but retention time is advantageously lower, and is general in 6～20 hours scope.For oxidation of pyrite, use the extraction temperature higher, but the concentrate that ought be supplied to this method is generally arrived ultra-fine level by fine grinding, during for example less than 10 microns, can save oxygen supply workshop section (this workshop section is used for pressure oxidation) than bio-oxidation.The structured material of treatment facility is the iron and steel and the titanium of fibre-reinforced plastics, liner rubber.
Arsenopyrite+pyrite+carbon (dual infusibility)
In the processing of gold ore, the effect of carbon is its content and active function basically.In the lower scope of carbon content, use organic additive (sequestering agent) to suppress gold absorption, perhaps in leach liquor, add activated carbon preferentially adsorbed gold (carbon in the CIL-leach liquor).In these situations, the oxidation of arsenopyrite is described earlier like this.
But when carbon content began to surpass 3～5%, along with " rich solution reclaims (preg-robbing) " increase of so-called gold, the effect of inhibition or CIL reduced greatly.Calcining destruction carbon has been the main processing selecting scheme of carrying out in the prior art in this case.Owing to extract the influence that gold is subjected to calcination condition from the calcinate that obtains, this is quite complicated method.And pyrite incinerating optimal conditions is different from those conditions of arsenopyrite, and it needs the two-section calcining process.
Use IRGP optionally to leach arsenic and sulphur before the calcining, to simplify calcining subsequently, in this case, it becomes simple more single stage method.And, because significantly reduced As
2O
3And SO
2, therefore remove the load that arsenic and sulphur have reduced the waste gas washing in the calcination operation.Therefore, consequently greatly reduce fund input and process cost in the calcining step.
First kind and second kind of processing scheme
When handling infusibility sulfide, in first kind of processing scheme of the present invention, use halogenide medium can make sulfide oxidation and gold dissolving carry out (so-called " single stage method (all-in-one) " process) simultaneously with certain solution oxide current potential.In second kind of processing scheme of the present invention, use the halogenide medium of different solutions parameter that oxidation of impurities (for example arsenic etc.) is occurred in before the sulfide oxidation, generally follow the dissolving of part gold to separate, and then carry out the gold recovery individually with impurity.Describe first kind of processing scheme of the present invention now in detail, describe second kind of processing scheme of the present invention afterwards in detail.
First kind of processing side examined
When describing first kind of processing scheme, with reference to Fig. 2～4 and embodiment 1～3.
Referring now to Fig. 2, Fig. 2 has schematically described the removal process 10 of single infusibility pyrite gold.Exploitation is ground, and the flotation sulfide mineral is supplied the precious metal concentrate 12 of this method with preparation then.Concentrate generally is auriferous arsenopyrite (when high-carbon content, it becomes dual infusible).In special ball mill, pulverize concentrate, general to ultra-fine level less than 10 μ m.Be supplied to arsenopyrite to leach the first leaching stage of stages 14 form in the concentrate of pulverizing then.
In arsenopyrite leaching process 14, keep sour environment (preferably less than 1, because the leaching that under low pH value of solution, can improve arsenopyrite).Can only depend on solution circulated to obtain sour environment, perhaps add the acid (for example sulfuric acid and hydrochloric acid) that does not have impurity.Generally keep infusion solution Eh greater than 0.4 volt, with the oxidation of the arsenopyrite composition that promotes described raw material and the dissolving of gold.Extraction temperature maintains about 80～95 ℃.
Then the raw material that leaches is delivered to second pyrite and leach the stage 16, add oxygenant (for example oxygen, air, chlorine, hydrogen peroxide etc.) here with raising solution oxide current potential, thus oxidation pyrite.In order to keep arsenic in the second leaching stage is precipitation forms, need to add acid (for example sulfuric acid) or alkali (for example lime carbonate) to keep pH value of solution about more than 0.2.
Treatment soln generally is the aqueous solution of cupric chloride, and its chloride concentration is 8 mol.At arsenic with in pyritous two leaching stages, cupric ion oxidation of sulfureted raw material, and be reduced to cuprous ion (equation (2) and (8)).Reclaimed copper ion in the acidic oxidation environment (equation (3) and (9)).So in the method, copper plays a part electron transfer agents, with Cu
2+/ Cu
+Ion pair exists.Other reagent also can play this function, comprises iron, cobalt, manganese, vanadium etc.
When sulfidic materials has high-carbon content (for example being up to 3～5%), the masked surface promoting agent can be joined the stage 14 and 16 to be adsorbed onto on the carbon with the gold (or other precious metal) that prevents to leach in the solution.Tensio-active agent generally is for example kerosene, a phenolic ether etc. of organic sequestering agent.Alternatively, can add gac preferentially adsorbed gold, and then remove.
In first kind of scheme, leach in the stage 14 at arsenopyrite, the inventor has been found that, less than 1, but be higher than under the pH value of arsenic dissolved control, under the quite moderate Eh of the control of about 0.7～0.8 volt (with respect to SHE) and under lower temperature (80～95 ℃), can leach raw material, and make the gold dissolving, and be not vitriol pyritous sulfide oxidation.
Leaching in the stage 16 employed oxidizing condition at pyrite, to leach the stage 14 than arsenic harsh more.About this point, to solution, make oxidizing potential Eh be increased to about 0.85 volt oxidant injection.In addition, the solution temperature in the second leaching stage need be brought up to about 90～105 ℃.And in first kind of scheme, control the second pH value of solution value that leaches the stage again less than 1, but be higher than arsenic dissolved pH value.
Because consumption acids in the leaching process of subordinate phase (that is, during regeneration Cu (II)), so give the solution supply acid periodically or continuously at leaching stages 16 needs, for example sulfuric acid, hydrochloric acid or other acid of not disturbing this process chemistry to react.But the adding of acid depends on pyrite and leaches whether produce enough sulfuric acid.In addition, in the leaching stage 16, prevent the arsenic dissolving by adding lime carbonate control pH value.
In the leaching stage 16, the sulfide complete oxidation is a vitriol, and iron leaches into (equation (1)) in the solution as Fe (III), in general all dissolvings of remaining gold (or other precious metal) in the pyrite.The contriver observes amazedly, in the presence of oxygen, in halide solution, at Cu
2+And Fe
3+Influence under, in the zone of 850mV (with respect to SHE), can obtain oxidizing potential.Since the formation of gold-chloro-complex, this current potential for gold at employed 8M Cl
-Dissolving is enough in the medium.
The solid slurry that obtains from the pyrite leaching stage 16 flows to solid-liquid separation phase 18, filters out solid at the known filter plant of this general use from solution.The liquid filtrate 20 that obtains flows to the precious metal recovery stage 22 of tandem, and filtering solid 24 discards as waste residue.Add that part of water that entry compensation and waste residue lose together in the stage 18.
The metal recovery stage 22 comprises one or more posts of filling gac, and solution is from bottom to top by post, for example in the thermopnore mode.Dissolved gold in the solution (or other precious metal) is adsorbed onto on the charcoal, and overflowing liquid stream 26 flows out post simultaneously, is recycled to the leaching stage 14.Remove or handle the gac that carries gold then periodically, flow to golden removal process (for example calcine charcoal product or with cyanide solution elution activated carbon column) as golden product flow 28.
The iron precipitate phase that overflowing liquid stream 26 is regulated stages 30 form through solution is recycled to the leaching stage 14.In the stage 30, add Wingdale and lime carbonate and form rhombohedral iron ore and gypsum, with the solubility ferric sulfate of precipitation, from this process, remove desulfuration and iron (equation (6)) from the oxidation of pyrite stage 16.The iron of about 2g/L in the solution is kept in the adding of control Wingdale, to prevent the cupric precipitation.Before discarding waste residue, filter out rhombohedral iron ore/gypsum slurry, and debris.Then solution circulated is returned the stage 14.
In order to prevent that impurity from accumulating in whole process, the part 32 of this logistics 26 is reclaimed as discharge stream 34, with removing foreign matter for example Mn, Cd, Ni, Co etc. (for example controlling precipitation) by improving the discharging pH value of solution.
The embodiment of first kind of processing scheme
Described after the preferred flow process, then described the preferred embodiment that is used for explaining first kind of processing scheme of the present invention.
As preliminary assessment, extract gold and carry out with three kinds of different steps from first kind of concentrate: arsenopyrite leaching, pyrite leaching 1 and pyrite leach 2.The method and the result of this three step described in following laboratory test report.CON1 01 is meant that arsenopyrite leaches and oxidation of pyrite 1, and CON1 02 is meant oxidation of pyrite 2.First kind of concentrate is ground to P80=30 μ, and carry out arsenic and leach, then be oxidation of pyrite.
Purpose
Purpose is that IRGP is applied on the single infusibility Au concentrate.Smelting the laboratory to wet method provides a mineral samplers, so that grind and concentrate.
Method
This test divides two portions to carry out, and carries out in 7.5 liters titanium insulation jar.First part uses common mixing machine to leach arsenic.Second section uses flat blade turbine and atomizer oxidation pyrite.
First part: arsenic leaches
In being furnished with 7.5 liters of titanium reactors of propeller type stirrer, prepare 3.5 liters the NaCl that contains 200g/L, the CaCl of 50g/L
2And the neutral brine of pH＜0.5.And prepare 5 liters the NaCl that contains 200g/L, the CaCl of 50g/L
2With the Cu of 75g/L (from CuCl
2) and " (boost) boosts " solution of pH＜0.5.As required, the dendrite copper that adds several grams with Eh be adjusted to 580 and 600mV between.The described solution that boosts maintains 80 ℃.
To leach reactor and be heated to after 105 ℃, the dry concentrate that will equal 300 grams is added in this salt solution.After 15 minutes, as required, spissated HCl is added to regulates pH＜0.5 in this suspension, take out the sample of t=0.Write down the adding (volume in the time of adding, volume, the batch extractor) of all acid.
Measure Eh and pH, slowly add the solution that boosts,, detect Eh in order to be no more than 530mV with the speed of 2.5L/h.Get a solution example in per 30 minutes and analyze As, Fe, Cu.Eh of detection in per 30 minutes and pH.
When Eh arrives 530mV and stablizes, think that the leaching of arsenic is finished.Filter this slurry.Washing this filter cake twice with hot salt brine (NaCl of 50g/L and pH＜1.0), then use hot wash, is limpid up to filtrate.Spend the night at baking oven inner drying filter cake.Analyze the S of filter cake
(T), S
(E), As, Fe, Au and C.
Second section: oxidation of pyrite
7.5 being equipped with, the reactor that rises goes up flat blade turbine agitator and titanium spraying organ pipe.10 liters of salt brine solutions of preparation in batch extractor, this solution contains the NaCl of 200g/L, the CaCl of 50g/L
2With the Cu of 75g/L (from CuCl
2), and add spissated HCl and make pH＜0.5 for 8.8 moles.Solution is heated to 105 ℃, gets the sample of t=0, the dry cake of producing during first part's arsenic is leached is incorporated in the jar.After 15 minutes, take out a solution example and measure Eh and pH.As required, add industrial HCl and make pH＜0.5.
Speed with 2L/min (rise/minute) is introduced oxygen; Detect Eh and pH every 30 minutes, per hour get sample analysis Fe, an As, Cu.When the Fe more than Eh is stabilized in about 600mV in 3 hours and the solution is constant, thinks to leach and finish.Filter this slurry.Washing this filter cake twice with hot salt brine (NaCl of 50g/L and pH＜1.0), then use hot wash, is limpid up to filtrate.Spend the night at baking oven inner drying filter cake.Analyze the S of filter cake
(T), S
(E), As, Fe, Au and C.
Concentrate resistates to embodiment 1 carries out oxidation of pyrite once more.
Purpose
The data of embodiment 1 and the analysis revealed of resistates, when test stopped, oxidation of pyrite was not fully.Present method is used improved salt solution prescription, attempts to use dioxygen oxidation pyrite to increase the extracted amount of gold.
The result
As shown in the table, oxidation of pyrite has been improved METAL EXTRACTION (based on independently analyzing) for the second time:
| | Oxidation | 1 | |
| As | 79.6％ | 92.4％ | |
| Fe | 72.2％ | 97.1％ | |
| Au | 68.7％ | 93.3％ |
Method
7.5 being equipped with, the reactor that rises goes up flat blade turbine agitator and titanium atomizer.Prepare 5 liters salt brine solution in batch extractor, this solution contains the NaCl of 100g/L, the CaCl of 250g/L
2With the Cu of 100g/L (from CuCl
2), and add spissated HCl and make pH＜0.5.Solution is heated to 105 ℃, gets the sample of t=0, the dry cake that the arsenic leaching/oxidation of pyrite of embodiment 1 is produced is incorporated in the jar.After 15 minutes, take out a solution example and measure Eh and pH.Add dense HCl as required and make pH＜0.5.
Speed with 2L/min is introduced oxygen; Detect Eh and pH every 30 minutes, per hour get sample analysis As, a Fe, Cu.When the Fe more than Eh is stabilized in about 600mV in 3 hours and the solution does not change, interrupt Oxygen Flow, detect Eh.When Eh rests on 600mV when above, think that oxidation of pyrite finishes.
Filter this slurry.Washing this filter cake twice with hot salt brine (NaCl of 50g/L and Ph＜1.0), then use hot wash, is limpid up to filtrate.Spend the night at baking oven inner drying filter cake.Analyze the S of filter cake
(T), S
(E), As, Fe, Au and C.
The result
Obtain following result from the test of embodiment 1 and 2.
| Time hour | Temperature ℃ | Eh mV | pH | Fe accumulates g | As accumulates g | Fe g/l | As g/l | ||
| Arsenopyrite leaches | 0.0 | 105 | Slightly | ||||||
| 0.3 | 105 | Slightly | 0.4 | 2.5 | 0.0 | 2.5 | 0.00 | ||
| 0.7 | 105 | 505 | ＜0.5 | 2.8 | 0.00 | 2.8 | 0.00 | ||
| 1.2 | 105 | 512 | ＜0.5 | 3.3 | 0.00 | 3.3 | 0.00 | ||
| 1.6 | 105 | 518 | ＜0.5 | 3.6 | 0.00 | 3.6 | 0.00 | ||
| 2.1 | 105 | 527 | ＜0.5 | 4.0 | 4.16 | 4.0 | 0.42 | ||
| 2.4 | 105 | 525 | ＜0.5 | 4.3 | 4.11 | 4.3 | 0.41 | ||
| 2.9 | 105 | 528 | ＜0.5 | 4.4 | 4.12 | 4.4 | 0.41 | ||
| 3.4 | 105 | 531 | 0.2 | 5.0 | 4.20 | 5.0 | 0.42 | ||
| Oxidation of pyrite 1 | 0.25 | 3.7 | 105 | 580 | 0.4 | 6.0 | 4.20 | 1.0 | 0.00 |
| 1.25 | 4.7 | 602 | 0.5 | 7.8 | 4.20 | 2.9 | 0.00 | ||
| 2.25 | 5.7 | 105 | 606 | 0.6 | 9.6 | 4.20 | 4.6 | 0.00 | |
| 3.25 | 6.7 | 105 | 597 | 0.5 | 12.0 | 9.20 | 7.0 | 0.50 | |
| 4.25 | 7.7 | 105 | 602 | 0.5 | 15.0 | 9.20 | 10.0 | 0.50 | |
| 5.25 | 8.7 | 607 | 0.4 | 17.0 | 9.70 | 12.0 | 0.55 | ||
| 6.25 | 9.7 | 105 | 606 | 0.5 | 18.5 | 9.20 | 13.5 | 0.50 | |
| 6.75 | 10.2 | 105 | 620 | 0.5 | 18.5 | 9.20 | 13.5 | 0.50 | |
| 9.75 | 13.2 | 105 | 609 | 0.7 | 21.2 | 11.20 | 16.3 | 0.70 | |
| 10.75 | 14.2 | 100 | 616 | 0.7 | 22.7 | 11.70 | 17.8 | 0.75 | |
| 11.75 | 15.2 | 100 | 616 | 0.6 | 24.7 | 12.20 | 19.8 | 0.80 | |
| 12.75 | 16.2 | 105 | 612 | 0.6 | 26.2 | 13.20 | 21.3 | 0.90 | |
| 13.75 | 17.2 | 105 | 623 | 0.6 | 26.7 | 13.20 | 21.8 | 0.90 | |
| 15.75 | 19.2 | 105 | 625 | 0.6 | 28.5 | 13.20 | 23.5 | 0.90 | |
| Oxidation of pyrite 2 | 0.75 | 19.9 | 105 | 661 | 0.2 | 29.6 | 13.20 | 0.5 | 0.00 |
| 1.75 | 20.9 | 105 | 661 | 0.2 | 31.7 | 13.20 | 1.5 | 0.00 | |
| 2.75 | 21.9 | 105 | 661 | 0.3 | 32.8 | 13.20 | 2.0 | 0.00 | |
| 3.75 | 22.9 | 105 | 674 | 0.3 | 33.9 | 13.20 | 2.5 | 0.00 | |
| 4.75 | 23.9 | 105 | 664 | 0.5 | 36.1 | 13.20 | 3.5 | 0.00 | |
| 5.75 | 24.9 | 104 | 665 | 0.4 | 37.2 | 13.20 | 4.0 | 0.00 | |
| 7.25 | 26.4 | 102 | 670 | 0.4 | 38.3 | 13.20 | 4.5 | 0.00 | |
| 8.25 | 27.4 | 104 | 675 | 0.4 | 39.4 | 13.20 | 5.0 | 0.00 | |
| 9.25 | 28.4 | 103 | 673 | 0.3 | 39.4 | 13.20 | 5.0 | 0.00 | |
| 10.25 | 29.4 | 103 | 671 | 0.4 | 40.5 | 13.20 | 5.5 | 0.00 | |
| 12.25 | 31.4 | 105 | 669 | 0.7 | 41.6 | 13.20 | 6.0 | 0.00 | |
| 13.25 | 32.4 | 105 | 673 | 0.7 | 41.6 | 13.20 | 6.0 | 0.00 | |
| 13.75 | 32.9 | 105 | 664 | 0.8 | 41.6 | 13.20 | 6.0 | 0.00 |
Gold extracts the result and is illustrated among Fig. 3.
In this test, golden: the pyrite leaching that step 1 arsenopyrite and pyrite leach, step 2 is used chlorine with the pyrite leaching and the step 3 of oxygen with three consecutive steps realization extractions from second concentrate.
Purpose
According to the exploratory experiment that arsenic is leached, present method is intended to use CaCl
2The salt solution of 250g/L and Cu 100g/L is handled second concentrate in " single stage method " process.Solids loading is set in 200g/L.
The result
As shown in the table, chlorine oxidation has improved golden extracted amount (based on the analysis of outside):
| The extraction (accumulation) of gold | |
| Air+oxygen | 59％ |
| Chlorine | 87％ |
| All | 95％ |
Method
In 7.5 liters of reactors that are equipped with turbine agitator, carry out this method.With 5 liters of salt solution of following formulation: NaCl 100g/L, CaCl
2250g/L and Cu 100g/L add dense HCl and regulate pH＜0.5.
First part: arsenopyrite leaches
At agitator speed (rpm) is 90% time, and salt solution is heated to 90 ℃.Take out of the reference of the sample of solution as future.Exsiccant " (as-received) that the former state obtains " concentrate (80% about 37 μ) that will equal 1000g joins in the described salt solution.Take out the sample of t=0, record Eh and pH after 15 minutes.
Speed with 2L/min is incorporated into air in the reactor.Every Eh of detection in 30 minutes and pH, sample thief is analyzed As, Fe simultaneously.When the Eh in the solution and Fe stablize, interrupt airflow.If Eh descends greater than 20mV, continued introducing air 2 hours.Be not more than 20mV when Eh descends, take out the solid sample of about 100g, air is switched to oxygen.
Second section: oxidation of pyrite
Temperature is increased to 105 ℃.Sampling and mensuration frequency shift are 1 hour interval.Speed with 2L/min under turbine agitator is introduced oxygen.When Eh in the solution and Fe stablize, interrupt oxygen.If Eh descends greater than 20mV, continue to introduce oxygen 2 hours.Be not more than 20mV when Eh descends, think that this method finishes.
Filter this suspension,, then use hot wash, up to obtaining limpid filtrate with acid brine washing leaching cake twice.The filter cake of dry washing is also weighed.Analyze As, Fe, Cu, element S, total S and the Au of resistates.And analyze the Au of final solution example.
Third part: pyrite chlorination
In order to improve the extracted amount of gold, use hypochlorite test to be extended to the pyrite chlorination as the chlorine source.The pyritous resistates of dioxygen oxidation is incorporated in 4 liters the salt solution of above-mentioned same composition.Temperature is elevated to more than 100 ℃, and per 30 minutes time adds the hypochlorite of 50g.Detect the concentration of Fe.Fe concentration no longer increases when stablizing with Eh after adding hypochlorite, thinks that this test finishes.
Filter this suspension,, then use hot wash, up to obtaining limpid filtrate with acid brine washing leaching cake twice.The filter cake of dry washing is also weighed.Analyze As, Fe, Cu, element S, total S and the Au of resistates.And analyze the Au of final solution example.
The result
| Time | Eh | pH | Fe | Total Fe | |
| Hour | mV | g/l | g | ||
| Air | 1.1 | 464 | 0.41 | 11.2 | 56.0g |
| 2.0 | 479 | 0.36 | 18.9 | 94.5g | |
| 3.0 | 470 | 0.23 | 20.3 | 101.5g | |
| 4.0 | 477 | 0.49 | 19.8 | 99.0g | |
| 5.0 | 473 | 0.49 | 18.9 | 94.5g | |
| 6.5 | 473 | 0.41 | 20.2 | 101.0g | |
| 7.5 | 472 | 0.53 | 22.4 | 112.0g | |
| 8.5 | 474 | 0.05 | 22.0 | 105.6g | |
| 9.5 | 473 | 0.53 | 20.0 | 100.0g | |
| 10.5 | 482 | 0.61 | 20.4 | 112.2g | |
| 12.0 | 494 | 0.38 | 21.4 | 117.7g | |
| 13.0 | 485 | 0.71 | 21.0 | 115.5g | |
| 14.0 | 492 | 0.65 | 20.3 | 111.7g | |
| 15.0 | 491 | 0.71 | 22.0 | 121.0g | |
| 17.0 | 500 | 0.22 | 23.0 | 124.2g | |
| 18.0 | 501 | 0.52 | 20.6 | 109.2g | |
| 21.0 | 517 | 0.15 | 23.3 | 121.2g | |
| Oxygen | 22.5 | 522 | 0.59 | 21.3 | 106.5g |
| 23.5 | 537 | 0.64 | 18.7 | 93.5g | |
| 24.5 | 552 | 0.64 | 16.3 | 81.5g | |
| 26.0 | 571 | 0.86 | 14.3 | 71.5g | |
| 27.0 | 613 | 0.69 | 14.8 | 74.0g | |
| 28.0 | 645 | 0.73 | 15.8 | 79.0g | |
| Hypochlorite | 28.5 | 630 | 0.77 | 16.2 | 164.8g |
| 31.0 | 661 | 0.35 | 17.7 | 172.7g | |
| 32.5 | 660 | 0.40 | 17.8 | 173.2g | |
| 33.5 | 691 | 0.10 | 18.0 | 174.3g | |
| 34.5 | 667 | ＜0.1 | 21.7 | 193.9g | |
| 35.5 | 664 | ＜0.1 | 21.3 | 191.8g | |
| 37.0 | 667 | ＜0.1 | 21.7 | 193.9g | |
| 39.0 | 684 | Slightly | 23.5 | 203.4g | |
| 40.0 | Slightly | Slightly | 21.3 | 191.8g |
The extraction result of gold is illustrated among Fig. 4.
Second kind of processing scheme
Before the mode with embodiment describes second kind of processing scheme in detail, second kind of processing scheme briefly described with reference to Fig. 5.
In Fig. 5, exploitation is ground, and the flotation sulfide mineral is supplied the precious metal concentrate 10 of this method with preparation then.In second kind of processing scheme, concentrate can be a high-carbon content (for example carbon of 2～20 weight %) or low or do not have the auriferous arsenopyrite ore deposit of carbon content (for example less than 2 weight %).In ball mill 12, pulverize concentrate, be supplied to the oxidation of impurities stage of arsenic leaching process 14 forms then.
Below with reference to Fig. 6 and 7 and embodiment 11 and 12 preferred arsenic leaching process is described in further detail.Leaching can be carried out in the single stage (for example having one or more processing units, container or jar), but generally carries out in many (two) section process.Each stage can have so that also stream or adverse current leach one or more processing units, container or the jar of formal operations, use overflow and underflow (as is known).
In every look condition, in leaching process 14, keep peracidity environment (, being favourable) from arsenopyrite because arsenic leaches under low pH value of solution preferably less than pH 1.Can only depend on the sulfidic materials oxidation to obtain sour environment (for example when the sulphur of raw material is oxidized to vitriol in solution) and/or add the acid (for example sulfuric acid or hydrochloric acid) do not have impurity.
And in second kind of processing scheme, generally infusion solution Eh is maintained greater than 0.4 volt of (see figure 8) with dissolved impurity (for example arsenic).With reference to Fig. 6 and 7 and the description of embodiment, leaching process has two stages as following.In first leaching stage, carefully control solution E h promoting the arsenic oxidation and the dissolving of+3 oxidation state, rather than solvability relatively poor+5 attitudes, the pyrite in the arsenic oxide arsenoxide pyrite raw material not basically simultaneously.In second leaching stage, add the oxidizing potential that oxygenant (for example oxygen, air, chlorine, hydrogen peroxide etc.) improves solution, thus oxidation pyrite (simultaneously remaining arsenic being oxidized to+5 oxidation state).In second kind of processing scheme, in second leaching stage, can reduce pH value of solution by the adding of controlling acid, to dissolve arsenic fully, thereby (V) maintains in the solution with arsenic, perhaps it maintained precipitation forms, makes it and pyrite resistates separate from this process.
Equally, treatment soln generally is the aqueous solution of cupric chloride, the chloride concentration that preferably has 7～8 mol.And copper serves as leaching agent and electron transfer agents.
Equally, when sulfidic materials has high-carbon content (for example greater than 2 weight %), can in solution, add the masked surface promoting agent, be adsorbed onto on the carbon with the precious metal that prevents to leach in the solution in the stage 14.
At the pH of acid less than 1 o'clock, under the Eh of the control in 0.4～1.25 volt of scope, preferred about 0.5 volt down, arsenic is oxidized to be leached in the solution, is preferably easily molten+3 oxidation state, and pyrite is vulcanized the vitriol that thing is not oxidized to the interference solution properties.
In first leaching stage, leach arsenopyrite concentrate preset time (as following described in an embodiment), up to a certain amount of arsenic from the arsenopyrite raw material, leach (general in first leaching stage total amount about 85%, in second leaching stage, leach again total amount 10%).Suppose that resistates is separated, handle with common melting or calcining technology then, or discard (as following) that under any circumstance, the amount of leaching is generally by acceptable level decision remaining in the arsenopyrite raw material that leaches.Therefore, Here it is phrase " purified arsenopyrite " or " purified sulfidic materials " explanation.
Like this in second kind of processing scheme, adjust pH value of solution and Eh, make arsenic and multivalence species Cu (II) (from raw material oxidation and leach arsenic) the first leaching stage still in solution, and do not precipitate.
In addition, control this process operation condition, make when solid/liquid separation (from solution, isolating purified arsenopyrite solid), arsenic to be maintained in the solution, be supplied to the arsenic precipitate phase up to solution.In Fig. 5, schematically described the thickening stage 16.In the process of Fig. 6 and 7, after the first leaching stage, use this thickening stage.In the thickening stage 16, purified arsenopyrite solid flocculation (for example adding flocculation agent) to it, solid settlement is a underflow 18, the aaerosol solution that contains arsenic and precious metal is separated into overflow 20 in the thickening stage.In Fig. 5, underflow or slurry 18 flow to the solid/liquid separation stage 22 then, generally use known filter plant to filter out solid from solution.
The liquid filtrate 24 that obtains turns back to overflow 20, and filtering solid (being the purified arsenopyrite) 26 flows to common calcination stage 28 and common prussiate leaches the stage 30, to reclaim remaining precious metal as golden product 32.
Leach according to arsenic that precious metal leaches degree in the stage 14, gold (with other precious metal) and blended liquid stream 34 (mixture flow 20 and 24) flow to recovery in the precious metal recovery stage 36 of tandem together.Recovery stage comprises the post of one or more filling gacs, and solution upwards flows through in the mode of thermopnore.Dissolved gold in the solution (or other precious metal) is adsorbed onto on the gac, and dissolved arsenic passes through this post as upper strata liquid stream 38 in the solution.Then the gac of load gold is regularly removed, as golden product stream 40 (with golden product stream 32 together) deliver to golden removal process (for example calcining and this activated carbon product of elution).
Solution 38 (comprising dissolved arsenic) is delivered to the contamination precipitation stage of arsenic precipitate phase 42 forms from the metal recovery stage 36.Stage 42 is generally in 1.5～3 times operations of pH.In the stage 42, oxygenant (for example air, oxygen, chlorine etc.) is introduced (for example spraying) in solution, improve solution oxide current potential (Eh), make dissolved arsenic form precipitation, it (is FeAsO that in general insoluble ferric arsenate precipitates
4Or scorodite).When impurity for example comprised antimony, impurity may be the tripuhyite of insoluble form.When contamination precipitation formed, general generation acid can add the alkali consumption acids like this, and keep preferred pH value of solution and Eh.Alkali is generally basic salt for example lime carbonate, calcium oxide etc., and it also has the advantage of the vitriol in the precipitation process liquid.
In second kind of processing scheme, in the contamination precipitation stage 42, adjust the adding of oxygenant and alkali and keep preferred pH and Eh level, up to all contamination precipitations.After this, as required, pH value of solution and Eh level are returned to the level in leaching stage 14, make and after contamination precipitation, solution circulated can be returned the leaching stage.
And in the precipitate phase of second kind of processing scheme, oxygenant makes cuprous ion be oxidized to cupric ion, and these species of having regenerated like this can circulate and utilization again.Therefore, adjust pH value of solution and Eh and advantageously promote reoxidizing of multivalence species, simultaneously it is all maintained in the solution at any time, therefore in whole process, copper+1 oxidation state and+change between 2 oxidation state, serve as electron transfer agent and participate in leaching.The regeneration of multivalence species has improved the economy of this method, has simplified this method, makes this method conservation of matter be accomplished.
After the arsenic precipitation, the arsenic throw out is separated from treatment solution in the solid/liquid separation stage.Described the stage of thickening again 44 among Fig. 5,, flow to solid-liquid separation phase 48 then to produce solid (arsenic throw out) underflow 46.Suspension liquid overflow 50 is overflowed from the top in thickening stage 44.In solids-liquid separation step 48, generally use filter plant to filter out the arsenic throw out, produce useless arsenic product 52.Filtrate turns back to overflow 50 as liquid stream 54.Mixed solution stream 56 flows to for example activated carbon column etc. of precious metal recovery stage 58, not have the metal of recovery to be recovered in the stage 36.Alternatively, can the 58 replacement stages 36 of operational phase.Precious metal that obtains and gac logistics 60 and other precious metal returned logistics 40 and 32 mix, and solution overflow 62 simultaneously loops back arsenic and leaches the stage 14, reclaim circulation to finish this processing.
In order to handle the impurity that is accumulated in the whole process, the part of recycle stream 62 is recycled to effluent streams 64, there are not the impurity that reclaims and optionally any other impurity for example Mn, Cd, Ni, Co etc. to isolate the arsenic precipitate phase.
Since briefly described second kind of processing scheme, with reference to Fig. 6 and 7 preferred second kind of processing scheme flow process described so.
Fig. 6 represents to handle the schema of single infusibility sulfidic materials.In Fig. 6, use similar or identical process stage in the identical reference number presentation graphs 5.With the similar fashion of Fig. 5 process, preparation 10 and to pulverize 12 carbon contents low or do not have an auriferous arsenopyrite ore deposit concentrate (being single infusibility ore deposit) of carbon.Then the concentrate of pulverizing is supplied to preferred leaching process.Preferred leaching process has two stages, i.e. first arsenopyrite (FeAsS) the leaching stage 70 and the second pyrite (FeS
2) the leaching stage 72.
The arsenopyrite concentrate was supplied to for the first leaching stage 70, wherein controls leaching condition and make basically arsenic in the oxidation concentrate only, and leach in the solution, and pyrite not oxidation of composition and leaching in the concentrate.About this point, the leaching condition of controlling in the first leaching stage 70 makes oxidizing potential Eh be about 0.5 volt, and pH value of solution is less than 1, and solution temperature maintains about 105 ℃ (although can operate) in the scope between 80 ℃ and 105 ℃.The contriver has observed these conditions, arsenic is leached in the solution optimize.Discuss in embodiment 11 as following, after about 6 hours leaching, about 85% of the total arsenic in the arsenopyrite concentrate leaches in the solution.
When the arsenic of predetermined amount leached in the solution, the arsenopyrite of solution and refining arsenic flow to the thickening stage 16 with the similar fashion of the process that Fig. 5 describes.The flocculation of purified arsenopyrite solid, sedimentation is a underflow 18, and arsenical aaerosol solution overflows the thickening stage to arsenic precipitate phase 42 as overflow logistics 20.
In second kind of processing scheme, purified arsenopyrite solids stream 18 flow to for the second leaching stage 72 now to leach pyrite.The oxidizing condition in the second leaching stage is stricter than the first leaching stage.About this point,, make oxidizing potential Eh be increased at least 0.6 volt, generally greater than 0.8 volt to solution jet paraffin oxidation agent oxygen for example.In addition, in the second leaching stage temperature maintenance of solution at about 105 ℃.The pH of solution still maintains below 1 in the second leaching stage.
Because consumption acids in the subordinate phase leaching process (being that Cu (II) and Fe (III) are reduced to Cu (I) and Fe (II) respectively), so need to give periodically or continuously solution supply acid, for example sulfuric acid, hydrochloric acid and other not acid of interfering process chemical reaction.Whether pyrite produces enough sulfuric acid but the adding demand of acid depends on leaching.As required, keep low pH in the second leaching stage and also help to dissolve As (V).
Leach the stage sulfidic materials second and be oxidized to vitriol, iron leaches in the solution with Fe (III), and the part of remaining arsenic also leaches in the solution in the arsenopyrite mineral.The contriver has observed and has had 10% of total arsenic to leach in the solution, make the final residual arsenic of leaching process be in the concentrate raw material total amount 5% or be lower than 5%.This equals to discard safely the enough low arsenic level of this process resistates.
Be similar to Fig. 5, the leach liquor in the second leaching stage 72 flows to solids-liquid separation step 22 as logistics 74, wherein, filters out residual solid from solution, and filtrate logistics 24 is returned and overflow logistics 20 mixing flow to arsenic precipitate phase 42.The solid residue that leaches in the stage 22 flows to waste residue as logistics 76, logistics 76 or for the solid that filters out or be slurry.Also can further handle solid and reclaim remaining metal.Can add entry in the stage 22 keeps the water-content of this process and/or replenishes the water that loses together with the process resistates.
In single infusibility arsenopyrite raw material and pyrite raw material, gold or other precious metal are not complexed on the carbon with significant degree, generally like this can leach in the solution in the first and second leaching stages, therefore can reclaim in the circulation of process.
In the process of Fig. 6, in arsenic precipitate phase 42, the pH regulator of solution adds for example air or oxygen of oxygenant, so that arsenic is oxidized to insoluble+5 attitudes from soluble+ 3 attitudes to about 2～3 (for example adding lime carbonate) in solution.Advantageously, because being present in from second, leaches in the solution of stage oxidation of pyrite, Fe (III) so arsenic is precipitated as scorodite (FeAsO
4).Also advantageously,, add lime carbonate and improve pH value of solution, and be calcium sulfate sulfate precipitation so can use at the arsenic precipitate phase because sulfide is oxidized to vitriol in the second leaching stage.
Arsenic/solid sediment and treatment solution flow to solids-liquid separation step 48 as logistics 78 together, filter out solid here from solution.Solid residue logistics 80 generally comprises the FeAsO that is fit to the form of discarding (for example burying)
4, Fe
2O
3And CaSO
4Solid is removed as slurry, after this adds the water that replenishes for this process in the stage 48.Like this arsenic, iron and sulphur can be advantageously from primary arsenopyrite concentrate the form with easy disposal reclaim.
The condition of arsenic precipitate phase does not influence in the leaching stage and leaches into precious metal in the solution, and therefore isolating solution 56 can flow to precious metal recovery stage 58 in the mode of the process that is similar to Fig. 5 now.Stage 58 comprises the post of one or more filling gacs, and precious metal (particularly gold) is adsorbed onto on it, removes golden product stream 60 to reclaim gold (gac of calcining or elution ADSORPTION OF GOLD on it) from the stage 58 termly.
As the process of Fig. 5, be recycled to the leaching stage from the solution overflow 62 in stage 58, a part of recycle stream can be extracted into effluent streams 64, isolate the impurity that is accumulated in this process, thereby produce impurity byproduct streams 82.
In second kind of processing scheme, shunting solution circulated logistics 62 leaches the step cycle component 84 and the second leaching step cycle component 86 to produce first.For the cupric chloride treatment solution, the copper of+2 oxidation state is recycled to each leaching stage participation first and leaches the pyrite leaching that the stage is leached in the arsenopyrite leaching and second in stage.
Referring now to Fig. 7, second kind of processing scheme schema handling dual infusibility sulfidic materials is described.In Fig. 7, use similar or identical process stage in the identical reference number presentation graphs 5 and 6.In addition, upper part of the method flow diagram of Fig. 7 (be dashdotted above) is identical with Fig. 6 in fact, the treatment stage of therefore no longer describing those.
In dual infusibility arsenopyrite, the general and carbon complexing of precious metal (for example gold), therefore the gold of complexing in the first or second leaching stage is not easy to leach in the solution.Therefore, solids stream 76 comprises the carbon/golden composition of solid residue and complexing.But, because the leaching stage is acceptable low-level except that going to arsenic, iron, sulphur and other impurity basically, so the solid residue of leaching process is highly suitable for calcination stage 28 calcining or meltings now.
In calcination stage 28, calcine air and fuel together with solid material 76 in the ordinary way, produce product stream 90, be supplied to the golden leaching stage 30 then in known manner.Generally the solid of crossing with chlorine or prussiate (but because chlorine is littler than prussiate toxicity, so preferred chlorine) oxidizing roasting carries out the gold leaching.In second kind of processing scheme, the part 92 of the solution circulated logistics of arsenic precipitate phase 42 is supplied to the golden leaching stage 30, to increase the economy of whole process.
To (generally comprise carbonic acid gas, sulfurous gas and other SO from the exhaust flow 94 of calcination stage 28
xGas) be supplied to the preliminary purge of gas stage 96.The preliminary purge of gas stage generally comprises one or more gas scrubbers, and wherein water contacts with gas stream 94 with selectable circulation cleaning water.Advantageously, can filter dust in the gas stream 94.This dust comprises gold trichloride (AuCl
3) and arsenic oxide arsenoxide (As
2O
3).This dust and other particle are supplied back arsenic precipitate phase 42 with solid or in solution as logistics 98 together, so that further reclaim arsenic and gold.
Residual gas from the preliminary purge of gas stage 96 flow to for the second purge of gas stage 102 as logistics 100, and this stage generally comprises gas scrubber, here, and the lime carbonate in the solution and contain SO
xGas contact.Therefore the product stream 104 in the second purge of gas stage 102 generally comprises calcium sulfate and calcium sulfite.
Now, the leach liquor logistics 106 that contains the dissolved gold that leaches the stage 30 from gold flows to solids-liquid separation step 108, so that isolate auriferous solution from solid residue.Solid residue logistics 110 flows to waste residue and is discarded, and auriferous solution flows to golden recovery stage 114, and golden recovery stage 114 generally comprises the post that contains gac.The gold of removing charcoal and absorption with logistics 116 termly to be reclaiming gold, and the solution 118 of poor gold is recycled to that leaching/arsenic is removed the loop and and logistics 34 mix.
The embodiment of second kind of processing scheme
Since described the optimization flow process of second kind of processing scheme, the preferred embodiment of second kind of processing scheme is described so now.In the following example, handle the high infusibility arsenopyrite concentrate of the Bakyrchik that takes from Kazakhstan.Its objective is a kind of method of exploitation, this method can be provided by all samples of the arsenopyrite that is provided by the Bakyrchik mine.
The sign of concentrate
Method:
Concentrate with ultra-fine secondary pulverization process 6kg.Described concentrate has 100% 20 micron particle sizes.
| Product | |
| The laser micron | The weight % that passes through |
| 20 | 100 |
| 18 | 99 |
| 15 | 96 |
| 12 | 89 |
| 10 | 81 |
| 8 | 69 |
| 6 | 50 |
| 5 | 42 |
| 3 | 15 |
Getting three blocky 100% is 20 microns concentrate, measures every moisture content, averages as the moisture content of this concentrate.
First
Wet sample+paper: 113.84g
Dry-eye disease+paper: 85.68g
Paper: 4.83g
Dry-eye disease: 80.85g
Moisture content: 25.8%
Second
Wet sample+paper: 88.35g
Dry-eye disease+paper: 66.65g
Paper: 4.83g
Dry-eye disease: 62.02g
Moisture content: 25.9%
The 3rd
Wet sample+paper: 86.41g
Dry-eye disease+paper: 68.79g
Paper: 4.85g
Dry-eye disease: 63.94g
Moisture content: 21.6%
The average moisture content of measuring is 24.4%.Can calculate from this, the dried concentrate conversion of 100g is the wet concentrate sample of 132.3g.
Oxidation is leached
Then to P
100=20 microns secondary is pulverized sample and is tested, with the Prima Facie Evidence that provides arsenic to leach with oxidising process.Notice that the concentrate in Bakyrchik ore deposit contains the arsenic of arsenopyrite form.The design reaction is to determine whether use+divalent copper can extract this arsenic and dissolve (therefore can optionally remove) as oxygenant.
Method:
Prepare 1 liter contain 80g/L Cu
2+(CuCl
2205.13g), 100g/L CaCl
2, 200g/LNaCl and 30g/L NaBr solution.The wet concentrate (～24% moisture, so the dried concentrate of 105.8g) of 140g is joined in this solution, stir the slurry that obtains down at 105 ℃.At four hours period detecting pH, Eh and Fe and Cu content.
Use Bu Shi (Buckner) equipment to cross filter solid subsequently, preserve filtrate so that further analyze.With salt solution (pH 0.3 for～0.5L, 280g/L) the washing solid filter cake of low pH, the wet cake that weighing obtains, dry in baking oven, weigh again.Preserve the exsiccant solid so that further analyze.
Result and discussion
Ji Lu pH, Eh and Fe and Cu content are summarised in the following table in time.
| Time (minute) | pH | Eh(mV) | Fe(g/L) | Total Cu (g/L) |
| 0 | ||||
| 30 | 1.45 | 740 | 2.4 | 70.6 |
| 60 | 0.5 | 508 | 2.5 | 68 |
| 90 | 0.5 | 507 | 2.5 | 63 |
| 150 | 0.5 | 495 | 2.65 | 64 |
| 210 | 0.35 | 502 | 2.65 | 61 |
| 270 | 0.35 | 495 | 2.68 | 64 |
| 330 | 0.35 | 485 | 2.66 | 65 |
The resistates analysis report shows that As concentration is 0.66%.The mass loss of considering calculating is 6.5% o'clock, and the leaching efficiency of As is 82.3%.
Reaction table reveals fast and carries out.In first hour of reaction process, observe Eh and pH obviously descends.After this time, stable reaction does not show progress again.
Oxidation is leached
Whether the purpose of this embodiment is to investigate fresh liquid to impel iron/arsenic further to leach from the raw material that leached the front.Conclusion is that processing is leached resulting solid from the front and can also be removed more arsenopyrite.Make the fresh solution of each initial liquid, use the raw material that leached to repeat previous leaching as solid material.
Method:
Prepare 500 milliliters and contain 80g/L Cu
2+(CuCl
2102.55g), 100g/L CaCl
2, 200g/L NaCl and 30g/L NaBr solution.The concentrate of the leaching that the oxidation of 30g front is obtained joins in this solution, stirs the slurries that obtain down at 105 ℃.At four hours period detecting pH, Eh and Fe and Cu content.Use Bu Shi equipment to cross filter solid subsequently, preserve filtrate so that further analyze.With salt solution (pH 0.3 for～0.5L, 280g/L) the washing solid filter cake of low pH, the wet cake of weighing and obtaining, dry in baking oven, weigh again.Preserve the exsiccant solid so that further analyze.
From solid and the sampling of primary concentrate that this reaction and the reaction of front obtain, use chloroazotic acid/these samples of perchloric acid boiling.Use the arsenic of these solution of icp analysis then.
Result and discussion
Ji Lu pH, Eh are summarised in the following table in time.
| Time (minute) | pH | Eh(mV) |
| 0 | 1.32 | 741 |
| 0 | 1.2 | 615 |
| 30 | 0.55 | 588 |
| 60 | 0.31 | 583 |
| 90 | 0.29 | 580 |
| 120 | - | 579 |
| 150 | 0.31 | 569 |
| 180 | 0.3 | 574 |
| 210 | 0.29 | 574 |
| 240 | 0.32 | 572 |
Wet cake+paper+filter paper: 72.5g
Dried filter cake+paper+filter paper: 40.24g
Paper+filter paper: 11.5g
The dried filter cake that obtains: 28.74g
The icp analysis result who reclaims arsenic in the solid is summarised in the following table:
| As | ||
| Content | Extract | |
| (weight %) | (percentage ratio of As in the concentrate) | |
| The Bakyrchik concentrate | 3.49 | 0 |
| Leach for the first time | 0.66 | 82.3 |
| Leach for the second time | 0.42 | 88.9 |
Observe from top leaching, reaction table reveals fast and carries out, and is stable through one hour time.When with join solution in solid masses compare, along with the decline of reclaiming solid masses, observe the obvious decline of Eh and pH again.This shows that having the material that still can extract has stayed in the resistates that leaches for the first time.Express from the arsenic content analysis result of the solid residue of raw material and this twice leaching and to reclaim solid arsenic content and gradually reduce.The result shows that can improve this method optionally leaches the arsenic that contains in the Bakyrchik concentrate.
Oxidation is leached
The purpose of this embodiment is to improve to leach the employed condition of arsenic from the Bakyrchik mineral.Successfully leached arsenical～65% of Bakyrchik mineral, improved this method and obtain bigger leaching performance.This method concentrates on two aspects: at first, leach liquor is simplified, and the second, under all temps and beginning pH, react to determine that these change improving the influence of leaching efficiency.
Method:
Prepare 5 liters and contain 80g/L Cu
2+(CuCl
21025.64g), 150g/L CaCl
2(750g) and the solution of 150g/L NaCl (750g), be heated to 80 ℃.The solution that then this solution is divided into three parts of 1.5L, every part of solution carries out oxidation to the wet concentrate (～24% moisture, so the dried concentrate of 108g) that is equivalent to 142.86g under different condition.
Oxidation infusion solution 1: leach and under 80 ℃, carry out
Oxidation infusion solution 2: leach and under 100 ℃, carry out
Oxidation infusion solution 3: leach and under 80 ℃, carry out.Beginning pH＜0.4, Eh＞550mV
In 2.5 hours time, measure the pH and the Eh of these solution.Get the sample of each discontinuously, analyze their iron and copper content.
Then use Bu Shi equipment to cross filter solid, preserve filtrate so that further analyze.With salt solution (pH 0.3 for～1L, 280g/L) the washing solid filter cake of low pH, the wet cake of weighing and obtaining, dry in baking oven, weigh again.Preserve the exsiccant solid so that further analyze.
From solid and the sampling of original concentrate that each reaction obtains, arsenic, copper and iron in the icp analysis sample are used in boiling.
Result and discussion
1 (80 ℃) liquor analysis is leached in oxidation
| Time (minute) | pH | Eh(mV) | Cu(g/L) | Fe (g/L) | The As of ICP (ppm) | Remarks |
| 0 | 2.15 | 720 | The solid that adds | |||
| 0 | 1.58 | 568 | 71 | - | - | |
| 30 | 0.95 | 535 | 77 | 0.79 | 824 | |
| 60 | 0.75 | 525 | 77 | 1.14 | 1033 | |
| 90 | 0.70 | 520 | 75 | 1.28 | 1152 | |
| 120 | 0.70 | 520 | 75 | 1.41 | 1216 | |
| 150 | 0.70 | 516 | 74 | 1.53 | 1308 |
Wet cake+paper+filter paper: 173.24g
Dried filter cake+paper+filter paper: 105.48g
Paper+filter paper: 11.5g
The dried filter cake that obtains: 93.98g
2 (100 ℃) liquor analysis is leached in oxidation
| Time (minute) | pH | Eh(mV) | Cu(g/L) | Fe (g/L) | The As of ICP (ppm) | Remarks |
| 0 | 1.88 | 735 | The solid that adds | |||
| 0 | 1.5 | 561 | 71 | - | - | |
| 30 | 1.1 | 525 | 79 | 1.75 | 1473 | |
| 60 | 1.05 | 528 | 79 | 1.85 | 1532 | |
| 90 | 0.98 | 529 | 80 | 2.0 | 1636 | |
| 120 | 0.94 | 525 | 84 | 2.0 | 1678 | |
| 150 | 0.89 | 528 | 85 | 2.14 | 1761 |
Wet cake+paper+filter paper: 170.3g
Dried filter cake+paper+filter paper: 113.32g
Paper+filter paper: 11.5g
The dried filter cake that obtains: 101.82g
3 (80 ℃, low pH) liquor analysis is leached in oxidation
| Time (minute) | pH | Eh (mV) | Cu (g/L) | Fe(g/L) | The As (ppm) that obtains by | Remarks | |
| 0 | 0.35 | 712 | The solid that adds | ||||
| 0 | 0.8 | 564 | 71 | - | - | ||
| 30 | 0.55 | 540 | 76 | 1.06 | 741 | ||
| 60 | 0.43 | 532 | 74 | 1.41 | 975 | ||
| 90 | 0.5 | 525 | 74 | 1.51 | 1082 | ||
| 120 | 0.4 | 520 | 75 | 1.61 | 1162 | ||
| 150 | 0.43 | 515 | 73 | 1.61 | 1181 |
Wet cake+paper+filter paper: 172.4g
Dried filter cake+paper+filter paper: 108.46g
Paper+filter paper: 11.5g
The dried filter cake that obtains: 96.96g
The icp analysis that reclaims arsenic, copper and iron in the solid is summarised in the following table.
| As％ | Cu％ | Fe％ | As extracts % | |
| Concentrate | 3.22 | 0.09 | 8.38 | 0.0 |
| Leach for the first time | 1.07 | 0.31 | 5.22 | 71.1 |
| Leach for the second time | 0.25 | 0.30 | 2.85 | 92.7 |
| Leach for the third time | 1.57 | 0.30 | 5.40 | 56.2 |
These results clearly illustrate that, speed of reaction at 100 ℃ apparently higher than 80 ℃.
The exclusion process of iron/arsenic
Method:
The liquid (10L) that obtains from the oxidizing reaction of front turns back to this groove, is being heated to 80 ℃ under slowly stirring.When arriving this temperature, measure the pH and the Eh of liquid, sampling.Stir down to this liquid aerating (100L/ hour), the pH and the Eh of mensuration liquid got a sample in per afterwards 30 minutes.Think after 4 hours that this exclusion process finishes, use Bu Shi equipment to filter this liquid, the precipitation that is excluded discards as filter cake.The wet cake of weighing, in baking oven dry 24 hours then.The dried filter cake of weighing then, the cooked sample analysis.
Result and discussion
Liquid pH and Eh and trend in time is summarised in the following table.
| Time (minute) | pH | Eh (mV) | Sample number | As (g/L) | Fe(g/L) | AAS Cu(g/L) | AAS Fe(g/L) | Remarks |
| 0 | 0.7 | 500 | 1 | 2.8 | 3.7 | 88 | 3.7 | Volume: |
| 0 | 0.7 | 500 | - | - | - | - | - | Air: 100L/ |
| 30 | 1.1 | 510 | 2 | 2.3 | 3.6 | 90 | 3.3 | |
| 60 | 1.5 | 520 | 3 | 1.2 | 2.7 | 90 | 2.6 | |
| 90 | 1.6 | 525 | 4 | 0.6 | 2.4 | 91 | 2.2 | |
| 120 | 2.0 | 530 | 5 | 0.3 | 1.3 | 85 | 1.6 | |
| 150 | 2.1 | 535 | - | - | - | - | - | |
| 180 | 2.1 | 545 | - | - | - | - | - | |
| 210 | 2.2 | 555 | - | - | - | - | - | |
| 240 | 2.5 | 570 | 6 | Do not detect | 0.5 | 88 | ＜0.1 | Total Cu 88, Cu 2+：88 |
Wet cake+paper+filter paper: 257.2g
Dried filter cake+paper+filter paper: 128.94g
Paper+filter paper: 11.5g
The dried filter cake that obtains: 117.44g
Sedimentary analytical results is illustrated in the following table:
| Element | Concentration |
| (weight %) | |
| As | 19.0％ |
| Fe | 33.8％ |
| Cu | 1.5％ |
In 4 hours test, 100% iron and arsenic precipitation returns to oxidizing potential (Eh) the higher further level of leaching that enough is used for that gets simultaneously basically.The molecular ratio of Fe/As is 2.4, can expect FeAsS and other compound coprecipitation based on Fe.
The exclusion process of iron/arsenic
Method:
The liquid (10L) that obtains from oxidizing reaction turns back to this groove, is heated to 80 ℃ under slowly stirring.When arriving this temperature, measure the pH and the Eh of liquid, sampling.Stir down to this liquid aerating (100L/h), the pH and the Eh of mensuration liquid got a sample in per afterwards 30 minutes.Think after 4 hours that this is given up process and finishes, use Bu Shi equipment to filter this liquid, the precipitation that is excluded discards as filter cake.The wet cake of weighing, in baking oven dry 24 hours then.The dried filter cake of weighing then, the cooked sample analysis.
Result and discussion
Liquid pH and Eh and trend in time is summarised in the following table.
| Time (hour) | pH | Eh (mV) | Sample number | As (g/L) | Fe (g/L) | AAS Cu(g/L) | AAS Fe(g/L) | Remarks |
| 0 | 0.7 | 500 | 1 | 2.8 | 3.7 | 88 | 3.7 | Volume: |
| 0 | 0.7 | 500 | - | - | - | - | - | Air: 100L/ |
| 30 | 1.1 | 510 | 2 | 2.3 | 3.6 | 90 | 3.3 | |
| 60 | 1.5 | 520 | 3 | 1.2 | 2.7 | 90 | 2.6 | |
| 90 | 1.6 | 525 | 4 | 0.6 | 2.4 | 91 | 2.2 | |
| 120 | 2.0 | 530 | 5 | 0.3 | 1.3 | 85 | 1.6 | |
| 150 | 2.1 | 535 | - | - | - | - | - | |
| 180 | 2.1 | 545 | - | - | - | - | - | |
| 210 | 2.2 | 555 | - | - | - | - | - | |
| 240 | 2.5 | 570 | 6 | Do not detect | 0.5 | 88 | ＜0.1 | Total Cu 88, Cu 2+：88 |
Wet cake+paper+filter paper: 257.2g
Dried filter cake+paper+filter paper: 128.94g
Paper+filter paper: 11.5g
The dried filter cake that obtains: 117.44g
Moisture: 128.26g (47.8%)
Leach lower slurry density with regenerated liquid
Method:
90g wet concentrate (～24% moisture, so the dried concentrate of 68g) sample is joined in the liquid (1.5L) that oxidizing reaction obtains, stir the slurries that obtain down at 100～105 ℃.The pH of tracer liquid and Eh in 4 hours time got a sample in per 30 minutes.After this time, use Bu Shi equipment filter liquide, remove filter cake, the weighing wet cake is then baking oven inner drying 24 hours.The dried filter cake of weighing then, the cooked sample analysis.
Result and discussion
Liquid pH and Eh and trend in time is summarised in the following table.
| Time (minute) | pH | Eh(mV) | Sample number | AAS Cu(g/L) | AAS Fe(g/L) | ICP As(g/L) | ICP Cu(g/L) | ICP Fe(g/L) |
| 0 | 2.5 | 600 | - | - | - | |||
| 10 | 1.8 | 555 | - | - | - | |||
| 30 | 1.5 | 550 | 1 | 90 | 1.5 | |||
| 60 | 1.3 | 545 | 2 | 89 | 1.1 | |||
| 90 | 1.2 | 540 | 3 | 87 | 1.2 | |||
| 120 | 1.1 | 540 | 4 | 67 | 0.8 | |||
| 150 | 1.1 | 535 | 5 | 88 | 1.0 | |||
| 180 | 1.0 | 535 | 6 | 85 | 1.0 | |||
| 210 | 1.0 | 535 | 7 | 88 | 1.0 | |||
| 240 | 1.0 | 536 | 8 | 87 | 1.1 |
The dried filter cake that obtains: 58g
First and second leach the embodiment in stage
Fs leaches
In this embodiment, purpose is to prove that by simulation successive process the operational condition that is used for batch test can be applied to industrial operation.This test also provides the raw material that is used for oxidation of pyrite under the normal atmosphere.
As shown in Figure 8, operate continuously has as one man obtained 85% arsenic and has extracted under the condition of the intermittent process of similar embodiment 5～7.
Method
Use 7.5 liters titanium reactor, be furnished with the upflow tube that is connected to second reactor from first reactor, overflow in the collector then.In operate continuously, use peristaltic pump solution to be supplied to first reactor from head tank with 2 liters of/hour speed.It is 144g/h (Grams Per Hour) that solid adds speed, adds 24g (butt) concentrate off and on and obtains this speed in per 10 minutes.
Prepare 30 liters the Cu that contains 80g/L during beginning
2+, the NaCl of 200g/L, the CaCl of 100g/L
2And the liquid storage of pH＜1.Add 7.5 liters liquid storage and maintain 100 ℃ to each reactor, the exsiccant that adds 360g equals the concentrate of the low gold content (30g/ ton) of P80=30 micron, stirs the slurry that obtains, detection in per 30 minutes Eh, pH, As, Fe and a Cu.After 3 hours, get the slurry sample of 100ml, filter, use the acid brine solution washing with B.Drying solid is used icp analysis copper, arsenic and iron then.
After 3 hours, carry out operate continuously (as describing) 10 hours again, per slurry sample of getting 200ml in 2 hours is as above-mentioned filtration.Drying solid is used icp analysis copper, arsenic and iron then.
The result is summarised in the following table.
First jar
| Numbering | Solid | Time | Sample | T | Eh | pH | Cu | Fe | As | Remarks |
| Sample | (minute) | (#) | (℃) | mV | (g/l) | (g/l) | (g/l) | |||
| 0 1 | 0 | 0 | 95 | 620 | 1 | 77 | 0 | 0 | The 720g solid that adds | |
| 2 | 60 | 1 | 100 | 520 | 0.5 | 87 | 2.6 | 2.3 | Below the wet concentrate of all reinforced being " former state " | |
| 3 | 12 0 | 2 | 100 | 520 | 0.5 | 83 | 2.7 | 2.3 | Add 192.95g in this | |
| 4 | 18 0 | 3 | 90 | 530 | 0.7 | 81 | 1.7 | 1.4 | Add 187.9g in this | |
| 5 | 24 0 | 4 | 98 | 535 | 0.6 | 88 | 1.9 | 1.6 | Add 183.4g in this | |
| 6 | 30 0 | 5 | 103 | 540 | 0.4 | 89 | 2.5 | 2.1 | Add 189.65g in this | |
| 7 | 1 | 36 0 | 6 | 109 | 530 | 0.2 | 74 | 2.2 | 1.9 | Add 195.44g in this |
| 8 | 42 0 | 7 | 109 | 535 | 0.2 | 95 | 3.7 | 3.3 | Add 194.42g in this | |
| 9 | 2 | 48 0 | Unstable | Condition | Add 31.61g in this | |||||
| 1 0 | 54 0 | 8 | 106 | 525 | 0.2 | 95 | 4.9 | 4.5 | Add 200g in this | |
| 1 1 | 60 0 | 9 | 102 | 524 | 0.3 | 95 | 4.2 | 3.8 | Add 198.79g in this | |
| 1 2 | 3 | 66 0 | 10 | 70 | 509 | 0.7 | 98 | 3.2 | 2.6 | Add 62.82g in this |
| 1 3 | 4 | 68 0 | 11 | 74 | 501 | 0.8 | 99 | 3 | 2.4 |
Second jar
| Numbering | Hour | Time | Sample | T | Eh | pH | Cu | Fe | As | |
| (minute) | (#) | (℃) | mV | (g/l) | (g/l) | (g/l) | ||||
| 0 1 | 0 | 0 | 80 | 620 | 1 | 77 | 0 | 0 | ||
| 2 | 60 | 1 | 85 | 530 | 0.9 | 77 | 1.3 | 1 | ||
| 3 | 120 | 2 | 86 | 530 | 0.8 | 81 | 1.5 | 1.2 | ||
| 4 | 180 | 3 | 90 | 530 | 0.7 | 84 | 1.7 | 1.5 | ||
| 5 | 240 | 4 | 88 | 530 | 0.6 | 86 | 1.8 | 1.6 | ||
| 6 | 300 | 5 | 85 | 525 | 0.5 | 91 | 2.1 | 1.8 | ||
| 7 | 1 | 360 | 6 | 85 | 520 | 0.4 | 95 | 2.2 | 2 | |
| 8 | 420 | 7 | 85 | 520 | 0.4 | 105 | 2.7 | 2.3 | ||
| 9 | 2 | 480 | | Condition | ||||||
| 10 | 540 | 8 | 84 | 519 | 0.4 | 99 | 2.8 | 2.5 | ||
| 11 | 600 | 9 | 83 | 514 | 0.4 | 98 | 3.2 | 2.9 | ||
| 12 | 3 | 660 | 10 | 83 | 516 | 0.4 | 98 | 3.5 | 3.1 | |
| 13 | 4 | 680 | 11 | 83 | 512 | 0.4 | 99 | 3.3 | 2.94 |
Solid analysis charging and second jar
| Sequence number | Explanation | Fe | As | Cu | As extracts | Mass loss | |
| (％) | (％) | (％) | (％) | (％) | |||
| Charging | 8.60 | 3.20 | 0.08 | 0.00 | 0.00 | ||
| 1 | Second jar | Solid 1 | 4.25 | 0.58 | 0.50 | 83.1 | 6.55 |
| 2 | Solid 2 | 4.15 | 0.42 | 0.52 | 87.8 | 6.79 | |
| 3 | Solid 3 | 4.55 | 0.51 | 0.55 | 85.1 | 6.27 | |
| 4 | Solid 4 | 4.15 | 0.51 | 0.42 | 85.1 | 6.80 | |
| Mixture | Solid 5 | 4.50 | 0.52 | 0.42 | 84.8 | 6.44 | |
| On average | 85.2 | 6.57 | |||||
Embodiment 12
Subordinate phase leaches
The purpose of this test is to estimate the possibility that under atmospheric pressure leaches the pyrite composition of resistates with the purity oxygen arsenic oxide arsenoxide.The 500g resistates that the continuous leaching test of use embodiment 11 obtains in this test.
Under normal atmosphere and 105 ℃ with the successfully oxidized pyrite of oxygen.Final arsenic and iron extract all more than 95%.The S of oxidation residues
(e)(elementary sulfur) equals the sulphur of arsenopyrite complexing in the concentrate.The result is diagrammatically shown in Fig. 9.
Method
On big yellow baking tray, prepare 7.5 liters of titanium reactors, this reactor is furnished with the turbine agitator of gas dispersion and suitable titanium matter gas syringe.5 liters of salt brine solutions of preparation in 7.5 liters of titanium reactors: 250g/L NaCl, 50g/L CaCl with following composition
2, 20g/L Cu (cupric chloride) and regulate pH＜1.0.
The exsiccant arsenic of embodiment 11 is leached the typical sample of resistates and deliver to the lab analysis element S of outside, total S, Au, Fe and As.
Go up setting stirrer-driven at vertical situation display (VSD) is 80Hz, and solution temperature is elevated to 105 ℃, gets the sample of t=0, detects Eh and pH, the 500g exsiccant arsenic of embodiment 11 is leached resistates be incorporated in the solution.After 30 minutes, get sample analysis Fe, As and Cu and the detection Eh and the pH of solution.
Speed with 1L/min is introduced oxygen.In preceding 3 hours, detected Eh, pH, Fe, Cu and an As in per 30 minutes, after this per hour detect once.When soluble Fe analytical results stops to increase, think to test and finish.
Get last sample, filtering suspension liquid with acid brine washing leaching cake twice, is used hot water then, is limpid up to filtrate.The filter cake of dry washing is weighed, and analyzes As, Fe, Cu, C, element S and total S.
Test-results
Observe following test-results.
Final leaching solid weight
Filter cake:
Wet cake+paper+filter paper: 744.27
Dried filter cake+paper+filter paper: 490.96
Paper+filter paper: 66.09
The dried filter cake that obtains: 424.87
Quality reduces: 15%
Solid analysis with the pyritous charging of dioxygen oxidation
Data are represented with dry weight % or ppm.
| Explanation | Fe | As | Cu | Au | Total S | Element S |
| (％) | (％) | (％) | ppm | (％) | (％) | |
| Total amount | 4.31 | 0.55 | 0.61 | - | - | - |
| Soluble | 0.01 | 0.03 | 0.10 | - | - | - |
| Insoluble | 4.30 | 0.51 | 0.51 |
Solid analysis with the pyritous resistates of dioxygen oxidation
Data are represented with dry weight % or ppm.
| Explanation | Fe | As | Cu | Au | Total S | Element S |
| (％) | (％) | (％) | ppm | (％) | (％) | |
| Total amount | 0.52 | 0.19 | 0.35 | - | - | - |
| Soluble | 0.01 | 0.01 | 0.01 | - | - | - |
| Insoluble | 0.51 | 0.18 | 0.34 | - | - | - |
From concentrate to the oxidation of pyrite resistatesFe
WithAs
Extract
As shown in the table, the extraction of As and Fe all surpasses 95%.
Oxidation of pyrite, charging and resistates
| Wt％ | Quality (g) | ||||
| Charging | | Charging | Resistates | ||
| 500 | 424.9 | ||||
| Fe | 4.3 | 0.51 | 21.6 | 2.2 | |
| As | 0.5 | 0.18 | 2.6 | 0.8 | |
The concentrate of equivalent
| Quality | Concentration | |
| (g) | (％) | |
| 535.2 | 100 | |
| As | 17.1g | 3.2 |
| FeAsS | 37.2 | 7.0 |
| Fe | 46.0 | 8.6 |
| FeS 2 | 25.6 | 4.8 |
| S | 29.4 | 5.5 |
| S among the FeAsS | 7.3 | 1.4 |
| FeS 2In S | 22.1 | 4.1 |
| Fe among the AsFeS | 12.8 | 2.4 |
| FeS 2In Fe | 19.3 | 3.6 |
| Other Fe | 14.0 | 2.6 |
Fe from concentrate to the oxidation of pyrite resistates and As extraction yield
| Fe | 95.3％ |
| As | 95.5％ |
The elementary sulfur that extracts from the oxidation of pyrite resistates shows S
(e)Equal and 1.4% of the S of AsFeS complexing or concentrate.
| Elementary sulfur extracts | ||
| The floating head example weight | 8.68 | 100％ |
| Extract the S resistates | ||
| Amount to | 0.35g | |
| Carbon | 0.21g | |
| S (e) | 0.14g | 1.6％ |
| Quality change | 79％ | |
| The S relevant with concentrate (e) | 1.28％ | |
Since given an example preferred process, the skilled personnel in this area can recognize that the present invention has following advantage:
Use present method to reclaim precious metal from sulfide mineral and concentrate, for example melting and calcining are difficult to maybe can not handle otherwise use common available method or technology.
Present method is applicable to these class mineral of high-carbon content, because present method is carried out in solution, can use sequestering agent to prevent that precious metal is adsorbed onto on the carbon, otherwise carbon will disturb precious metal to reclaim.
Use present method multi mineral and concentrate impurities in raw materials can be removed,, just can use common melting/calcining technology to handle in case remove impurity.
Present method can stay the easy to handle concentrate so that the form that discards is removed arsenic, iron and sulphur from original arsenopyrite concentrate.
Present method has the ability of the metal, particularly precious metal that reclaim multiple economically valuable, and this method is used simple non-leaching and sepn process based on prussiate, and comprises charcoal absorption.
Use present method can handle the resistates of pollution, can subsequently it be discarded and little environmental influence.
Although described the present invention with reference to many preferred versions, should be realized that the present invention can be embodied as many other forms.
Claims (39)
1. method that from sulfidic materials, reclaims precious metal, the method comprising the steps of:
Prepare a kind of acid halide aqueous solution, this solution has sufficient oxidizing potential with the oxidation of sulfureted raw material and make precious metal dissolve in this solution;
Sulfidic materials is added in this acid halide aqueous solution, makes sulfidic materials oxidation and make precious metal dissolving; With
Separate precious metal from the sulfidic materials of oxidation.
2. method that from the sulfidic materials of arsenic contamination, reclaims precious metal, the method comprising the steps of:
Prepare a kind of acid halide aqueous solution, this solution has sufficient oxidizing potential with the oxidation of sulfureted raw material and make precious metal dissolve in this solution, and this solution has the sedimentary pH value of the arsenic of making;
Sulfidic materials is added in this acid halide aqueous solution, makes the sulfidic materials oxidation, the precious metal dissolving, and make the arsenic precipitation; With
Separate precious metal from the sulfidic materials of oxidation and sedimentary arsenic.
3. method as claimed in claim 1 or 2 is wherein separated with the sulfidic materials of oxidation at the solution that solids-liquid separation step will contain precious metal, when having arsenic, also separates with sedimentary arsenic, reclaims precious metal in the metal recovery stage from solution then.
4. method as claimed in claim 3, wherein in the metal recovery stage, precious metal is adsorbed onto on the gac in one or more posts that contain carbon.
5. method as claimed in claim 4, wherein after precious metal was adsorbed onto on the gac, with the described gac of cyanide solution elution, eluant flow to electrolysis stage and reclaims precious metal.
6. as any described method in the claim 3～5, wherein tandem ground is equipped with the metal recovery stage after solids-liquid separation step and before solution circulated arrives the sulfidic materials oxidation.
7. as any described method in the claim of front, wherein the precious metal of Hui Shouing is the metal of gold and silver, platinum or other platinum family.
8. as any described method in the claim of front, wherein aqueous chloride solution is the soluble metal halide solution, and this solution has the halide concentration of about 8 mol.
9. method as claimed in claim 8, wherein halogenide is muriate or comprises muriate and the halid mixture of bromide.
10. method as claimed in claim 8 or 9, wherein, the solution metal of dissolved metal halide is copper and/or iron, and these metals play the multivalence species.
11. as any described method in the claim of front, wherein the sulfidic materials oxidation step comprises one or more leaching stages, makes:
(i) for untainted single infusibility pyrite raw material, the sulfidic materials oxidation step comprises the single leaching stage, in this stage pyrite raw material oxidation, and precious metal dissolving simultaneously; Or
(ii) for the single or dual infusibility pyrite raw material that pollutes, the sulfidic materials oxidation step comprises one two stage leaching process, and wherein first solution that leaches the stage was supplied to for the second leaching stage.
12. method as claimed in claim 11, wherein, for (ii), the pyrite raw material is an arsenopyrite, and controlled oxidation current potential in the first leaching stage, so that arsenic is leached into solution, and the control pH value of solution makes arsenic in case leach and just to be precipitated as ferric arsenate, and, in the second leaching stage, the pyrite composition leaches, and the control pH value of solution is the ferric arsenate throw out to keep arsenic, thereby makes the sulfidic materials of arsenic and oxidation tell from this process.
13. method as claimed in claim 12, wherein in the first leaching stage, raw material contacts with solution, this solution has about 0.7～0.8 volt Eh of enough leaching impurity and dissolving precious metal, the pH of this solution is less than 1 but greater than about 0.5, so that precipitation immediately after making arsenic leach, and about 80～105 ℃ of this solution temperature.
14. as claim 12 or 13 described methods, wherein in the second leaching stage, raw material contacts with solution, this solution has pyritous about 0.8～0.9 volt Eh of enough leachings, but the pH of this solution is less than 1 greater than about 0.2, so that precipitate immediately after making arsenic leach, and this solution temperature is about 90～105 ℃.
15. as any described method in the claim of front, wherein after precious metal reclaims, use solution adjusting stage sulfate precipitate iron, control the level of this material in this process thus.
16. method as claimed in claim 15 wherein, adds Wingdale and lime carbonate to form rhombohedral iron ore/gypsum deposition in solution in the solution adjusting stage, filter this precipitation then, the solid residue with the stage of leaching discards together then.
17. as any described method in the claim of front, wherein, when having high-load carbon in the sulfidic materials, adding tensio-active agent to solution in the sulfide oxidation step is adsorbed onto on the carbon in the raw material to prevent precious metal, or in the sulfide oxidation step, add gac to solution, preferentially precious metal is adsorbed onto on the gac.
18. method as claimed in claim 17, wherein tensio-active agent is one or more organic solvents, comprises kerosene or phenolic ether.
19. a method of removing impurity from the sulfidic materials that pollutes, the method comprising the steps of:
Described raw material is blended in the aqueous solution, wherein, the multivalence species oxidation impurities of the higher state of oxidation, so that impurity dissolves in this solution and produce the raw material of having removed impurity, and these multivalence species are reduced the lower state of oxidation; With
From solution, remove impurity, simultaneously these multivalence species are regenerated to the higher state of oxidation.
20. a method of removing impurity from the sulfidic materials that pollutes, the method comprising the steps of:
Described raw material is blended in the aqueous solution, and the oxidizing potential of this solution only is controlled as basically oxidation impurities so that impurity dissolves in this solution, thereby produces the raw material of having removed impurity; With
This solution is separated with the raw material of having removed impurity.
21. as claim 19 or 20 described methods, wherein precipitation takes place and remove impurity from solution by introducing oxygenant in the precipitation separation stage to solution.
22. method as claimed in claim 21, wherein in precipitate phase, pH value of solution generally maintains about pH 1.5～3.
23. as any described method in the claim 19～22, wherein impurity oxidation and leaching in the solution in two sections leaching process, wherein in the first leaching stage, the controlled oxidation current potential basically only oxidation impurities so that impurity dissolves in this solution, in the second leaching stage, increase oxidizing potential with oxidation removal the sulfide in the raw material of impurity.
24. method as claimed in claim 23, wherein, having removed the raw material of impurity separated from solution after the first leaching stage, and be supplied to for the second leaching stage, and, after each leaching stage, solution is separated with the raw material of having removed impurity, so that therefrom remove impurity by precipitation.
25. as claim 23 or 24 described methods, wherein sulfidic materials is the pyrite raw material, and in the first leaching stage impurity pH less than 1 acidic aqueous solution in oxidation, solution E h enough enters solution with oxidation of impurities, but does not leach pyrite basically, and temperature is up to about 105 ℃, in the second leaching stage, the pyrite raw material also pH less than 1 acidic aqueous solution in oxidation, but be in the higher pyritous solution E h of enough leachings, temperature is up to about 105 ℃.
26. method as claimed in claim 25 wherein in the second leaching stage, adds oxygenant for example oxygen, air, chlorine, hydrogen peroxide in solution.
27. as any described method in the claim 19～26, wherein solution circulates in whole process, and this solution is the dissolved solution of metal chloride, about 8 mol of its chloride concentration, and the metal in this dissolved solution of metal chloride plays the multivalence species.
28. as any described method in the claim 19～27, wherein have high-load carbon in the sulfidic materials, and when oxidation of impurities, add tensio-active agent, be adsorbed onto on the carbon in the raw material to prevent precious metal to solution.
29. as any described method in the claim 19～28, this method also comprises one or more metal recovery stages, so as to reclaim and impurity leaches in the solution together and/or the removal of remnants the metal that exists in the raw material of impurity.
30. method as claimed in claim 29, wherein sulfidic materials is the carbonaceous dual refractory mineral of bag, and after the last leaching stage, be equipped with a metal recovery stage, with reclaim remaining removal exist in the raw material of impurity be adsorbed onto metal on the carbon.
31. method as claimed in claim 30, wherein the metal recovery stage comprises common calcining or fusion process, optionally adopts halogenide or prussiate to leach after calcining or melting, so that reclaim remaining metal in the burnt solid material.
32., wherein before contamination precipitation and/or be equipped with a tandem metal recovery stage afterwards, leach into solution metal so that remove in the leaching stage as any described method in the claim 29～31.
33. as any described method of claim 29～32, wherein before metal recovery, be equipped with many raw material separation phases, from solution, to separate the raw material of having removed impurity.
34. method as claimed in claim 33, wherein, isolated solution flows to the impurity recovery stage after each leaching stage, and isolated refining raw material flows to the metal recovery stage or discards.
35., wherein after contamination precipitation, before solution circulated arrives the leaching stage, be equipped with the impurity separation phase from solution, to remove impurity as any described method of claim 23～34.
36. a processing has the sulfidic materials of pollution of higher carbon content to reclaim the method for the precious metal in the raw material, comprises step:
-in the aqueous solution, leach raw material, wherein metal leaches in the solution, and the carbon of sheltering simultaneously in the raw material is adsorbed onto on it to prevent precious metal; With
-from solution, reclaim precious metal.
37. method as claimed in claim 36 is wherein sheltered carbon with the tensio-active agent that claim 18 limited.
38. as claim 36 or 37 described methods, any limits in other aspects of this method such as the claim 1～35.
39. any metal of producing by any method in the aforementioned claim.
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| AU2002953566A AU2002953566A0 (en) | 2002-12-31 | 2002-12-31 | Removing contaminants from sulfidic materials |
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| AU2003903167 | 2003-06-20 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522925B (en) * | 2006-09-13 | 2011-03-16 | 恩派科技有限公司 | Oxidative and anoxic extraction of metals from sulphide minerals |
| CN103205580A (en) * | 2013-04-19 | 2013-07-17 | 金川集团股份有限公司 | Desulfurization method in noble metal enriching process |
| CN103540743A (en) * | 2012-07-13 | 2014-01-29 | 张超 | Hydrometallurgical method of metal sulfides |
| CN105378121A (en) * | 2013-04-30 | 2016-03-02 | 奥图泰(芬兰)公司 | Method of preparing a gold-containing solution and process arrangement for recovering gold and silver |
| CN107109528A (en) * | 2014-10-29 | 2017-08-29 | 奥图泰(芬兰)公司 | For the technique for reclaiming gold |
| CN108467948A (en) * | 2018-04-19 | 2018-08-31 | 上海泰坦科技股份有限公司 | A kind of palladium and its preparation method and application |
| CN109338406A (en) * | 2018-12-05 | 2019-02-15 | 昆明理工大学 | A kind of electroreduction metal sulfide method and device |
| CN110142565A (en) * | 2019-05-17 | 2019-08-20 | 湖北汉银精艺实业有限公司 | Impurity separation and removal process for high-density pure silver product |
| CN110573659A (en) * | 2017-04-27 | 2019-12-13 | 卡勒拉公司 | Electrochemical, chlorination and oxychlorination systems and methods of forming propylene oxide or ethylene oxide |
| CN112246445A (en) * | 2020-08-27 | 2021-01-22 | 中国恩菲工程技术有限公司 | Foam sorting activator and application thereof |
| CN116254410A (en) * | 2022-12-31 | 2023-06-13 | 贵州中伟资源循环产业发展有限公司 | Leaching method of sulfide minerals |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106990156B (en) * | 2017-06-08 | 2019-04-09 | 广西大学 | The electrochemical test method that Galvanic acts in sulfide flotation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU627603B2 (en) * | 1989-09-18 | 1992-08-27 | Geevor Del Ecuador C.A. | A method for gold recovery using chlorine dioxide solution |
| AUPP543798A0 (en) * | 1998-08-24 | 1998-09-17 | Technological Resources Pty Limited | Hydrometallurgical extraction of copper and other valuable metals |
| CN1079439C (en) * | 1999-11-11 | 2002-02-20 | 聂如林 | Process for cyanogen-free lixiviating of gold from gold-contained substances |
| WO2002042503A1 (en) * | 2000-11-21 | 2002-05-30 | Orthotech Industrial Corporation | Recovery of precious metals from carbonaceous refractory ores |
| ES2184630B1 (en) * | 2001-08-03 | 2004-01-16 | Soc Es Carburos Metalicos Sa | METHODS OF SELECTIVE LIXIVIATION OF METALS. |
-
2002
- 2002-12-31 AU AU2002953566A patent/AU2002953566A0/en not_active Abandoned
-
2003
- 2003-12-19 CN CNB2003801080516A patent/CN100344775C/en not_active Expired - Fee Related
- 2003-12-19 ZA ZA200505261A patent/ZA200505261B/en unknown
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522925B (en) * | 2006-09-13 | 2011-03-16 | 恩派科技有限公司 | Oxidative and anoxic extraction of metals from sulphide minerals |
| CN103540743A (en) * | 2012-07-13 | 2014-01-29 | 张超 | Hydrometallurgical method of metal sulfides |
| CN103540743B (en) * | 2012-07-13 | 2015-06-03 | 张超 | Hydrometallurgical method of metal sulfides |
| CN103205580A (en) * | 2013-04-19 | 2013-07-17 | 金川集团股份有限公司 | Desulfurization method in noble metal enriching process |
| CN105378121A (en) * | 2013-04-30 | 2016-03-02 | 奥图泰(芬兰)公司 | Method of preparing a gold-containing solution and process arrangement for recovering gold and silver |
| US10060007B2 (en) | 2013-04-30 | 2018-08-28 | Outotec (Finland) Oy | Method of preparing a gold-containing solution and process arrangement for recovering gold and silver |
| CN107109528A (en) * | 2014-10-29 | 2017-08-29 | 奥图泰(芬兰)公司 | For the technique for reclaiming gold |
| US10669608B2 (en) | 2014-10-29 | 2020-06-02 | Outotec (Finland) Oy | Process for recovering gold |
| CN107109528B (en) * | 2014-10-29 | 2019-07-23 | 奥图泰(芬兰)公司 | For recycling the technique of gold |
| CN110573659A (en) * | 2017-04-27 | 2019-12-13 | 卡勒拉公司 | Electrochemical, chlorination and oxychlorination systems and methods of forming propylene oxide or ethylene oxide |
| CN108467948B (en) * | 2018-04-19 | 2020-05-22 | 上海泰坦科技股份有限公司 | Palladium and preparation method and application thereof |
| CN108467948A (en) * | 2018-04-19 | 2018-08-31 | 上海泰坦科技股份有限公司 | A kind of palladium and its preparation method and application |
| CN109338406A (en) * | 2018-12-05 | 2019-02-15 | 昆明理工大学 | A kind of electroreduction metal sulfide method and device |
| CN110142565A (en) * | 2019-05-17 | 2019-08-20 | 湖北汉银精艺实业有限公司 | Impurity separation and removal process for high-density pure silver product |
| CN112246445A (en) * | 2020-08-27 | 2021-01-22 | 中国恩菲工程技术有限公司 | Foam sorting activator and application thereof |
| CN116254410A (en) * | 2022-12-31 | 2023-06-13 | 贵州中伟资源循环产业发展有限公司 | Leaching method of sulfide minerals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100344775C (en) | 2007-10-24 |
| AU2002953566A0 (en) | 2003-01-16 |
| ZA200505261B (en) | 2006-09-27 |
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