CN102459661A - Enhanced recovery of gold - Google Patents

Enhanced recovery of gold Download PDF

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Publication number
CN102459661A
CN102459661A CN2010800262678A CN201080026267A CN102459661A CN 102459661 A CN102459661 A CN 102459661A CN 2010800262678 A CN2010800262678 A CN 2010800262678A CN 201080026267 A CN201080026267 A CN 201080026267A CN 102459661 A CN102459661 A CN 102459661A
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Prior art keywords
nitric acid
gold
plumbous
insoluble
lead
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D·R·巴特勒
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Precious Metals Recovery Pty Ltd
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Precious Metals Recovery Pty Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/06—Chloridising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/08—Obtaining noble metals by cyaniding
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

An improved method for recovering refractory gold from a material comprises treating the material to at least partially remove nitric acid-insoluble lead moieties.

Description

The reinforcement of gold is reclaimed
Technical field
The present invention relates to the method for a kind of reinforcement from the gold recovery of material.Particularly, the present invention relates to the recovery of the indissoluble gold of common inapplicable cyanide process.In fact, because the existence of indissoluble gold is always not tangible, therefore the invention provides a kind of method of identifying and reclaiming indissoluble gold.
Background technology
Cyanide process is through being usually used in from starting material, reclaiming gold; Yet in some materials, a certain proportion of gold even most of golden content are not suitable for direct cyanide process.Ability suitably definite and the recovery indissoluble gold can be brought remarkable economic efficiency.The material that contains " difficulty is soaked " gold is that wherein at least some gold can't contain gold copper-base alloy (like ore or through the ore composition of processing) through what standard prussiate processing disengaged.These difficulties are soaked material needs pre-treatment to be used for cyaniding or to reclaim effectively other processing at gold usually.The instance of known refractory mineral comprises mineral, carbon containing ore that contains sulfide or the material that contains sulfide mineral and carbon simultaneously.Sulfide mineral is caught or the occlusion gold grain usually, and infusion solution is difficult to and golden complexing.The carbon that is present in the Gold Ore can adsorb dissolved gold-cyanide complex with the mode similar with gac, reduces the amount of the gold that can be reclaimed by leach liquor thus.The gold that exists but be not suitable for direct cyanide process is known as indissoluble gold.
The indissoluble gold material can comprise raw ore, washed ore, flotation concentrate, mine and technology mine tailing and prussiate mine tailing and residue.These materials possibly be that difficulty is soaked, and reason is precious metal and mineral bonding in ore, for example in silver-manganese dioxide ore silver maybe with the manganese bonding, directly cyanide process can not fully be broken this key.Starting material also can be that difficulty is soaked, because precious metal combines with other mineral or is encapsulated in other mineral.An instance of this situation is following situation: wherein precious metal is dispersed in the sulfide ore subtly, makes precious metal have only very little surface area exposure in the prussiate leach liquor.Can relate to hydrometallurgy or pyrometallurgy technology or the fine grinding before the cyaniding step by this ore recuperation precious metal.Said pre-treatment is designed and makes that indissoluble gold is easy in follow-up (normally prussiate) leaching step, dissolve.
The hydrometallurgical technology that improves the gold recovery comprises that use sulfuric acid, hydrochloric acid or nitric acid leach.Utilize the bacterial treatment raw material of oxidation of sulfureted ores also to be fine.The pyrometallurgy technology of improving the gold recovery comprises calcining, pressure oxidation and chlorination.The overwhelming majority of said technology relates to the matrix corrosion (and often being the matrix oxidation) of raw material.In other words, the major part that contains gold copper-base alloy is corroded with further recovery gold.The chemical conversion of matrix corrosion, matrix oxidation and/or body material has increased cost relevant with technology and refuse significantly, and possibly make said technology economically or unacceptable on the environment.In process stream, there is the body material that surpasses 20 weight % to be corroded usually or transforms through processing, thereby by disengaging indissoluble gold in this streams.
Gold can exist with part per million in ore, and this possibly make sampling error significantly increase.As everyone knows, when carrying out the gold analysis, even small inconsistent (for example, the high concentration of local zone of gold) in the raw material also can cause tangible error (this is called piece gold effect sometimes) when a plurality of samples of taking-up and to it.The method that a kind of maturation and practical definite indissoluble gold exist is the diagnostic lixiviation process.Diagnostic leaches by Lorenzen and Deventer at Minerals Engineering; The 6th volume; The 8-10 phase; Open in 1013-1023 (1993) " through of the evaluation (The Identification of Refractoriness in Gold Ores by the Selective Destruction of Minerals) of selectivity mineral failure " to the soaking property of difficulty of Gold Ore, through quoting its content is incorporated in this specification sheets.In the diagnostic lixiviation process, at first use selectivity (for example oxidisability) to leach and remove the special component in the sample, the precious metal that uses the cyanide process extraction to disengage then through the structure of destroying this component.Can in solution, measure the precious metal that is extracted, so that the record quite accurately with the amount of this component bonded heavy metal to be provided.In addition, all resistatess in this first leaching stage can carry out one or more other selectivity and leach stages, thereby destroy other components that may prevent the gold extraction.Between these stages, use at least a in diluted acid and the prussiate to wash also to can be used for the failure surface settling and to carrying out quantitatively through the indissoluble gold that is detained in the selectivity leaching destructive component.Can change this program to be fit to the mineralogy of body material (that is, containing gold copper-base alloy).Traditionally, will quote as the mark (for example, per-cent or part per million or other marks) of warp washing and exsiccant initial sample by the detected result that leach liquor obtains.In this way, all detected results all also can directly compare with reference to initial sample.
Diagnostic leaches and is not limited to ore and resistates, but can handle any kind intermediate product that occurs in factory.
Lorenzen and Deventer point out that a kind of leaching that diagnostic leaches in the sequence can be that nitric acid leaches, and follows by the cyaniding step.It is said that nitric acid can decompose all the mineral substrate materials beyond the desilicate, and some gold possibly continued to be locked among these silicate.Said silicate resistates is described to " final residual thing ", and this is all to be trapped in silicates basal body inside because it is believed that all other the gold in the sample.Typical diagnostic leaching program is:
(a) the cyaniding washing is to disengage precipitation of gold;
(b) cyaniding is leached to disengage free gold;
(c) the HCl/ cyaniding is to disengage and bonded gold such as pyrrhotite, calcite, ferrite;
(d) H 2SO 4/ cyaniding is to disengage and bonded gold such as unsettled cupric sulfide, unsettled pyrite, alkali metalsulphide, uraninite;
(e) HNO 3/ cyaniding is to disengage and pyrite, arsenopyrite, white pyrite bonded gold;
(f) between the stage pickling to disengage top coat; With
(g) the acetonitrile wash-out is to disengage the gold that is absorbed on carbon, petrologen, the coal.
Henley etc. are at Minerals Engineering (the 14th volume; The 1st phase; January calendar year 2001,1-12 page or leaf) described in " to the assessment (Evaluation of a diagnostic leaching technique for gold in native gold and gold/silver tellurides) of the diagnostic leaching-out technique of the gold that is used for natural gold and gold/silver-colored telluride " in 0.1% the prussiate of pH 9.5 for the time stage 1 of 24 hours leach and 2% prussiate at pH 12.5 in for the time stages 2 of 96 hours leach.
Goodall etc. are at Minerals Engineering (the 18th volume; The 10th phase; In August, 2005; The 1010-1019 page or leaf), described in " PIXE and diagnostic leach the application (Applications of PIXE and diagnostic leaching in the characterisation of complex gold ores) in the sign of complicated Gold Ore " and use various diagnostic to leach sequences to raw material to carry out proton-induced X-ray emission (PIXE) with sampling and analyze.From these researchs, can reach a conclusion, indissoluble gold possibly be locked in the sulfide matrix.
Resource Development Incorporated provides the diagnostic of customization to leach, and said diagnostic leaches and relates to progressive fierce more leaching and cyaniding between the stage, with displacing of gold in definite various mineral types.Celep etc. " are used for the application (Application of Diagnostic Leaching Technique for Refractory Gold Ores) of the diagnostic leaching-out technique of refractory gold ore " and mention diagnostic at DPU Fen Bilimleri Enstitusu 16 Sayi Eylul 2008 and leach the thin gold grain that can the soaking property of difficulty of ore be pinned in owing to carbonate, oxide compound, sulfide and silicate.
The key feature of diagnostic leaching-out technique is that the sign of raw material realizes in the following manner: the correlation analysis scheme that combines to be used for continuous leach liquor is specifically specified the leaching sequence.Because gold is present in the raw material with quite low weight fraction usually; Therefore before being designed to disengage the fiercer leaching step of more indissoluble gold, removing " being prone to obtain " gold earlier is the method that a kind of logical sign contains gold copper-base alloy with " being prone to obtain " body material, also is that probabilistic method (particularly can reduce when a kind of component in the material is disturbed the analysis of another kind of component possibly cause analysis difficulty) is analyzed in a kind of reduction.
Diagnostic leaches provides a kind of actual mechanism that is used to define the novel process step that can effectively discharge indissoluble gold.Diagnostic leaches a kind of mechanism that is used to characterize the feed composition that disturbs the gold recovery also is provided.In the prior art, said interfering component is considered to exist with respect to gold is obviously excessive (in the weight fraction in the raw material).For with as be lower than 1000 weight part per millions, particularly be lower than the processing of the low-level interfering components that exist such as 100 weight part per millions, the trial of being done is seldom.
In some cases, before finding to expose the existence of obscurant and removing the means of obscurant, the indissoluble gold that exists in the material maybe be undiscovered always.In these cases, the gold content of material possibly significantly covered or underestimated.
In a word, the diagnostic leaching comprises in the reason of the routine use of Jin Yezhong:
Avoid piece gold effect;
Reduce the interference in the routine analyzer;
Can characterize to cause and suppress golden Recycled materials; With
Through the clear and definite signal relevant with the influence of independent unit operation being provided and, can realizing the inline process exploitation to the combination relevant with the unit operation of the component that contains golden sample.
The discussion that comprises in this manual file, behavior, material, device and article etc. only is used to the purpose that the present invention provides background.Be not the common practise in hint or a part of or association area of the present invention of representing any or all these things formation prior art bases, because it promptly existed before priority date of each claim of the application.
Exist exploitation to be used for reclaiming the pretreated demand of disengaging indissoluble gold at present at gold analysis and gold.
Summary of the invention
The inventor has been found that in many cases can reclaim indissoluble gold through removing the obscurant that comprises the insoluble plumbous part of nitric acid.In containing the course of processing of gold copper-base alloy, removing this obscurant can be so that can reclaim gold with the yield greater than predicated value.
Therefore, the invention provides a kind of improving one's methods of indissoluble gold of from material, reclaiming, said method comprises that part is removed the insoluble plumbous part of nitric acid from material.
In one group of preferred implementation, this method comprises handles material so that the insoluble plumbous part of at least a portion nitric acid is converted into the plumbous part of leachability and leaches this material to remove the plumbous part that at least some have transformed.
Being suitable for will containing at least in part instance that the insoluble plumbous part of nitric acid in the gold copper-base alloy is converted into the method for the plumbous part of leachability comprises and contacting with a kind of reagent that is selected from by in reductive agent, molten plumbous agent and the group that plumbous complexing agent is formed containing gold copper-base alloy.This can be following situation; That is, be used to remove the insoluble plumbous part of nitric acid or be used for that the insoluble plumbous part of nitric acid is converted into the validity of the reagent of the plumbous part of leachability can be through (a) to containing golden raw material and provide vigorous stirring or cavitation to stir or (b) adopting the method for removing or partly remove the oxidation scale layer of remained on surface to strengthen.Said method can comprise utilizes thermal treatment to remove liquid and/or raw material is contacted with organic solvent from the raw material surface evaporation.
The inventor has been found that and utilizes ultrasonic agitation to remove the insoluble lead part of nitric acid or the insoluble plumbous plumbous ability partly of leachability that partly is converted into of nitric acid is effective especially for strengthening reagent.
The inventor finds that also the reagent that utilizes warp to heat is removed the insoluble lead part of nitric acid or the insoluble lead of nitric acid partly is converted into leachability lead ability partly for the said reagent of enhancing is effective.
Mentioned reagent can be gaseous state or liquid reagent.Gaseous reagent can be dissolved in the liquid vehicle, and can be stablized through said carrier is remained under the pressure.Gaseous reagent can comprise ammonia or other amine functionality materials.
If mentioned reagent is a liquid, then it can be a waterborne liquid.Waterborne liquid can provide reductibility environment or oxidative environment, perhaps both also non-oxidizing environment of irreducibility.In treating processes, the oxidizing potential of waterborne liquid can be from negative (reductibility) even be worth just (oxidisability) value variation of less negative value.As other a kind of selection, in treating processes, the oxidizing potential of liquid can be from just (oxidisability) even be worth less changing on the occasion of negative (reductibility) value.Irrelevant with the oxidizing potential of liquid, the pH of liquid can be acid, neutral or alkaline.
In a preferred implementation, waterborne liquid can comprise ammonium ion or comprise other ions of amine functional group.
Can use one or more continuous processings from raw material, to remove nitric acid insoluble part at least in part.
In a preferred implementation, before handling, from raw material, remove particulate at least in part, from raw material, to remove nitric acid insoluble part at least in part.In a preferred implementation; Particulate is removed in the following manner at least in part: the slurry of the raw material with 10%, discards overflow and collects raw material part in the underflow to be used for further processing through 2 inches Mozley wet cyclones at the input pressure of 350kPa.
Many relate to contain gold copper-base alloy and reductive agent, dissolve plumbous agent, method that plumbous complexing agent contacts is invalid removing aspect the insoluble plumbous part of nitric acid.This is because nitric acid is the powerful reagent of the plumbous part of extraction from sample.
The present invention provides a kind of evaluation to be used at least partly removing the suitable reagent of the insoluble plumbous part of nitric acid and the method for condition from sample.Suitable reagent and condition can utilize " the insoluble plumbous test that detects of nitric acid " described in this specification sheets to confirm.This test relates to: (a) the first step; Provide a plurality of nitric acid to leach step to sample; The plumbous level of dissolved is lower than 5ppm really, preferably is lower than that 1ppm (as the weight fraction of initial sample weight)---this will stay the final residual thing that does not contain nitric acid dissoluble lead part in final nitric acid leach liquor; (b) second step, the final residual thing is used candidate agent and condition---those promote from the final residual thing, to disengage the reagent plumbous above 1.5ppm and are regarded as with condition and can from sample, at least partly remove the insoluble plumbous part of nitric acid.
An importance of the present invention is that reagent of in above-mentioned test, identifying and condition can directly apply to raw material, as the processing that makes it possible to from raw material, reclaim indissoluble gold.
The instance of suitable reductive condition comprises through the reductive condition that provides with the liquid electrodes in contact, and/or the reductive condition through using reductive agent to provide, and/or the reductive condition through using the reductibility mikrobe to provide.
Preferably, reductive agent is selected from the reductive agent group with water compatible.Preferably, these reductive agents are selected from the group that comprises chromium (II), tin (II), copper (I), titanium (II) and titanium (III) part and comprise sulphite, sulfur-bearing reductive agent, oxalic acid and other organic reducing agents.
In a preferred implementation, suitable water-based reduced liquid will comprise tin (II) part, the more preferably form of tin protochloride.
In a preferred implementation, the water-based reduced liquid is a tart, and preferred pH is lower than 1.
Plumbous complexing agent or the instance that dissolves plumbous agent can be waterborne liquids, and said waterborne liquid comprises and is selected from the group of being made up of hydrochloric acid, nitric acid, basic metal (like sodium hydroxide or other oxyhydroxide parts) or the plumbous partly deliquescent reagent in water of other alkali, sugar of lead, ammonium chloride, muriate, carboxylic acid and salt thereof, sequestrant, silicofluoride, phenolsulfonate, peroxidation sulfuric acid hydrogen salt and any other enhanced oxidation with water compatible one or more.When plumbous complexing agent or dissolve plumbous agent when being selected from carboxylic acid and salt or muriate; Preferably; (a) carboxylic acid be selected from the group formed by Hydrocerol A, lactic acid, acetate, formic acid, isopropylformic acid, Xaxa and salt thereof (like an alkali metal salt and alkaline earth salt etc.) and (b) muriate be selected from the group of forming by ammonium chloride, sodium-chlor, Repone K, calcium chloride and strontium chloride.
In another group embodiment; A kind of method of confirming in suspection contains the material of indissoluble gold, to exist indissoluble gold is provided; Said method comprises sample separation from this material; This sample is suitable for from this sample, removing at least in part the processing of the insoluble plumbous part of nitric acid and treated sample is carried out gold analysis.
In this group embodiment; We find; When discharging, sample is lower than 1ppm when plumbous in last nitric acid leach liquor after a plurality of nitric acid leach steps; With remove when disengaging the resistates that the processing of the insoluble plumbous part of nitric acid forms that 1.5ppm is plumbous at least after nitric acid leaches sequence when being suitable at least part, this is that said processing will can make the indissoluble gold can effectively good indication aspect the analysis in sample.
Therefore, this method can comprise the existence of confirming indissoluble gold and handle material through the method that use is suitable for dissolving the insoluble plumbous part of nitric acid and reclaim indissoluble gold.
Embodiment
The inventor utilizes the diagnostic leaching method to learn to have studied many kinds and contains golden raw material.They utilize the diagnostic that comprises a series of nitric acid leachings to leach scheme and have studied raw material particularly.According to the prior art nomenclature, leach the resistates of handling from said a plurality of nitric acid and will be known as " final residual thing ".Prior art thinks that any gold that keeps in the final residual thing will be locked in the silica substrate, and can only come release to the method for the matrix corrosion of silica substrate through providing, and for example uses the processing of hydrofluoric acid.
The inventor has obtained surprising discovery, that is, indissoluble gold can combine plumbous part to be present in the final residual thing.Said plumbous part is not locked in the silica substrate, and it should be noted that they are insoluble to successive nitric acid and leach step---so they will be known as " the insoluble plumbous part of nitric acid ".The combining of the insoluble plumbous part of indissoluble gold and nitric acid do not identified in the past as yet.
Though it is very important for reclaiming indissoluble gold to remove the insoluble plumbous part of nitric acid at least in part, does not exist in the method for the invention and carries out the needs that nitric acid leaches step.Diagnostic leaches the existence that can be used for confirming the insoluble lead of nitric acid as required, can also be used to make an experiment be used for removing at least in part the reagent and the technology of the insoluble plumbous part of nitric acid with check.
Even the insoluble plumbous part of nitric acid exists with lower level with respect to nitric acid dissoluble lead part, they also have remarkably influenced for the ability that reclaims gold.For example; The inventor have been found that the insoluble plumbous part of nitric acid changes in leach liquor and during dissolving usually be lower than can nitric acid continuously leach the semi-invariant of the nitric acid dissoluble lead part that reclaim in the step 10%, as be lower than 5%, be lower than 2% and 1% the amount of being lower than exist.
Definition
" indissoluble gold material " refers to and can not handle the golden raw material that contains that reclaims through direct prussiate.
" indissoluble gold " refers to be present in the indissoluble gold raw material but is inappropriate for the gold of removing through direct cyanide process.The discussion of soaking raw material about difficulty is found in US 5232490 (Bender etc. submitted in 1992), through quoting its content is incorporated in this specification sheets.
" matrix corrosion pre-treatment " refers to like pre-treatment such as hydrometallurgy and dry process pre-treatment, and said pre-treatment causes the dissolving/erosion (surpass 15 weight %, surpass 20 weight % usually, calculate with respect to the weight through washing and exsiccant raw material) of most of raw material.
Term " the insoluble plumbous part of nitric acid " refers to leach insoluble plumbous part in the step at successive nitric acid.These parts reclaim in the technology at conventional gold can serve as obscurant.
Term " final nitric acid leaches resistates " and " finally leaching resistates " refer to the resistates that repeatedly leaches processing from this use nitric acid.
All of this specification sheets describe with claim in, word " comprises " (comprise) and the version (like comprising and comprises) of this speech and be not intended to other additives of eliminating, component, composition or step.
The inventor finds, the processing of removing the final residual thing of the insoluble plumbous part of nitric acid at least in part also can be used as the processing that is used to reclaim indissoluble gold or pre-treatment and directly applies to the material that is considered to contain indissoluble gold.
Do not hope to be subject to theory, the insoluble plumbous chemical property partly of nitric acid for the interference gold recovery that the inventor found it is believed that the part that comprises that term " poor sulphur lead sulfate " is contained.A kind of such part is the mineral yellow lead ore, yet it is believed that gold also can partly combine with other poor sulphur lead sulfates, and said part can be used as the anti-coating existence of dissolving and surrounding ultra-fine dispersive gold in the raw material.
Hereinafter described nitric acid is insoluble plumbously to be detected test and comes experimental material through using, and can select from given material, to remove at least in part reagent and the condition of the insoluble lead of nitric acid and need not carry out unsuitable experiment.In case confirmed to be used for removing at least in part the felicity condition of the insoluble plumbous part of nitric acid, just can use selection condition to process given material (that is, not adopting nitric acid to leach).
The insoluble plumbous test that detects of nitric acid
Part 1---be used to produce the diagnostic leaching program of standard final residual thing
Washing and dry size are usually less than 500 microns feed particulate material (CHECK).This material of 10g is inserted in the beaker of 600ml, and said beaker has the liquid that 200ml comprises 1 parts by volume water and 1 parts by volume concentrated nitric acid.Beaker is inserted power setting bathes in (the bath frequency is 42kHz) at 60 ℃ the thermostatic ultrasonic of 150 watts (that is, peak power 250 watts 60%).Applied ultrasonic agitation 1 hour, and next stopped 1 hour, and then opened ultrasonic agitation 1 hour, by that analogy, make the time add up to 8 hours.Filtration residue, and use flame atomic absorption spectrometry (flame AA) is then carried out the lead test to filtrating.According to above scheme, in 50% concentrated nitric acid, leach all resistatess once more, and once more filtrating is carried out lead analysis.Further leach, the lead in filtrating (with the also mark expression of the weight of exsiccant raw material of initial warp washing) is lower than 1ppm in the leaching step continuously at 2.Can use up to the leaching more than 9 times, the lead of in filtrating, finding leaches in the step continuously at 2 and is lower than 1ppm.
Part 2---be used for removing at least in part the evaluation of the insoluble plumbous candidate processes partly of nitric acid
Produce standard final residual thing as above part 1 is said by raw material, and the final residual thing that is obtained is used candidate processes.Final step in the candidate processes is that water-based leaches step.Filtering is used for water-based and leaches the liquid of step and use flame atomic absorption spectrometry that it is carried out lead analysis.If the lead in the filtrating (expressing with initial weight fraction through washing and exsiccant raw material) surpasses 1.5ppm, then be regarded as and confirmed that candidate is handled and from raw material, removed the insoluble plumbous part of nitric acid at least in part.The ability of diagnostic lixiviation process is, utilizes the order of same starting material sample to leach all aspects of confirming sign---particularly need not prepare two " same " material samples that are used for comparison.This has overcome the known problem that is known as piece gold effect---and promptly, when gold during with low-level the existence, the probability that local rich gold zone occurs in a sample can not duplicate in another sample.The analogue of piece gold effect also is applicable to and possibly exists and maybe be so that gold reclaims the other materials of the mode of being obstructed and metallographic pass with low-level.This low-level interfering material (for example, the insoluble plumbous part of nitric acid) also will receive piece gold effect, make that carrying out the definite trial of direct analysis produces indefinite result.Use diagnostic to leach the similar problem that golden effect is relevant that has also overcome with interfering material.An important execution preferred implementation of the present invention comprises uses the diagnostic lixiviation process to characterize the gold recycling.
Be used for confirming that candidate processes is converted into the insoluble plumbous part of raw material nitric acid the standard of nitric acid dissoluble lead part at least in part
Produce standard final residual thing by raw material as stated, and the final residual thing is used candidate processes.Then; At liquid that can soluble lead (for example; 50% aqueous nitric acid according to the scheme that in part, is provided) leaches the resistates that is obtained in, and utilize flame atomic absorption spectrometry or accepted method of equal value that filtrating is carried out lead analysis about diagnostic leaching program.If surpass 1.5ppm, then be regarded as and confirmed that this processing is converted into nitric acid dissoluble lead part with the insoluble plumbous part of nitric acid in the raw material at least in part at this final lead (weight fraction with initial washing and exsiccant raw material is expressed) that leaches in the rear filtrate.
The definition of " the sign property level of the insoluble plumbous part of nitric acid "
The total amount that is present in the insoluble plumbous part of nitric acid in the sample possibly be difficult to confirm with absolute and clear and definite mode, is difficult to confirm the same as the aggregate level of indissoluble gold in the sample.This be because, regardless of the amount of the insoluble plumbous part of the nitric acid that reclaims in the treated final residual thing from leach liquor, still can residual other amount in the resistates.Yet; The inventor finds; If standard final residual deposits yields is from material sample; Then use following liquid to the leaching of standard final residual thing (as above describe about the part of " diagnostic that is used for producing standard final residual thing leaches program " 60 ℃ of ultrasonic agitation) in leach liquor, disengage usually with before nitric acid and leach the obviously more lead of comparing that (being used to produce standard final residual thing) disengaged, said liquid makes through being added into the dense HCl of 100ml in the 100ml water and the 8g stannous chloride dihydrate being dissolved among the 50%HCl that is obtained.
More than before the lead (mark (with ppm) with initial washing and exsiccant raw material is expressed) that leaches available from acid/tin protochloride that leaches of nitric acid will reach the sign property level that hereinafter is known as the insoluble plumbous part of nitric acid in the raw material herein.The sign property level of the insoluble plumbous part of nitric acid is to leach the amount that program clearly defines according to diagnostic in the sample, but obviously the content of the insoluble plumbous part of acid in sample maybe be greater than this sign property level.
It is the common technology that is used to estimate the gold content of raw material that fire detects, and is the theme of Australian standards 2917.2 (1994) " fiery sense weight analysis and atomic absorption spectrometry (Fire assay gravimetric and atomic absorption spectrometric method) " and corresponding international standard.The golden yield that the existence of indissoluble gold obviously detects than fire through the golden yield of pointing out cyanide process usually lacks (in percentage ratio) to be proved.Fire detects usually through carrying out like specialized laboratories such as Australian Amdel laboratories.
In some cases, the inventor finds that the pre-treatment of from material, removing the insoluble plumbous part of nitric acid at least in part can obtain to detect the indicated higher recovery than the fire of material.
Therefore, the golden yield compared in detecting with the fire of raw material, pre-treatment can cause the recovery (in follow-up leaching or leach in the sequence) of more gold.
In one group of preferred implementation, present method comprises handles material so that the insoluble plumbous part of at least a portion nitric acid is converted into the plumbous part of leachability and leaches this material to remove the plumbous part that at least some have transformed.
In a preferred implementation; A kind of improving one's methods of indissoluble gold of from material, reclaiming is provided; Wherein raw material comprises the insoluble plumbous part of nitric acid of nitric acid dissoluble lead part and sign property level; And wherein nitric acid dissoluble lead part and the ratio of the insoluble plumbous part of nitric acid of sign property level are greater than 10: 1, more preferably greater than 100: 1.
In a preferred implementation, present method relates to the less corrosion (based on the weight of washing and exsiccant matrix) of treated matrix with the material of removing the insoluble plumbous part of nitric acid, and preferably is lower than 10%, as is lower than 5%, is lower than 2% and be lower than 1% etc.More not preferred matrix relates to those and experiences remarkable corrosive matrix.For example, use mineral acid will cause significant corrosion for the carbonate matrix.Particularly, preferable methods relates to the corrosion of comparing matrix with the identical leach liquor that does not have reduction components less (for example, leaching the inferior tin of the HCl/ that compares with independent HCl leaches).
In a preferred implementation, method of the present invention relates to uses reductibility waterborne liquid or reducing gas to handle raw material.The reduction leaching can cause removes base metal at least in part from raw material.Be not subject to theory, it is believed that the dissolving of using reduction to leach to promote the part that comprises iron (III) similarly, and these parts be to make the golden fixed origin cause of formation or the part origin cause of formation.The evidence that dissolving comprises the part of iron III comprises that leaching the back material decolours.Leaching can be carried out in comprising 1%HCl and the liquid like one or more reductive agents such as tin chloride (II), chromium chloride (II) and oxalic acid.Based on the degree of viewed decolouring, the validity of reductive agent reduces according to the ordering of tin chloride (II) >=chromium chloride (II)＞oxalic acid.
Referring now to following examples the present invention is described.Should be appreciated that embodiment provides so that mode of the present invention to be described, they do not limit the scope of the invention extremely.
Embodiment
Embodiment 1
What present embodiment showed is how to produce the final residual thing by raw material.
Obtain the thin Playa raw material of 1 weight part (below 100 microns) from closing on New Mexico Silver City,, make this slurry under 350kPa pressure, pass through 2 inches Mozley cyclonic separator then its furnishing slurry in water (10 weight part).Discard overflow, and under barometric point, filter underflow,, this resistates is placed in 80 ℃ the baking oven and spends the night, obtain in order to the desliming exsiccant of further processing material through washing to carry out drying to form moist resistates.
According to following scheme, under ultrasonic agitation, this material is carried out successive nitric acid and leaches step:
L1: 10g desliming washing and exsiccant Playa material are placed the beaker of 600ml, and said beaker has through the 100ml concentrated nitric acid being added into the liquid that makes in the 100ml water.Place the Soniclean thermostatic ultrasonic to bathe (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 1 hour, next stop 1 hour, opened then 1 hour, the rest may be inferred, makes the ultra sonic bath time add up to 8 hours.Use the slurry in No. 1 filter paper filtering beaker of Whatman, and take out filtrating and carry out lead analysis through atomic absorption spectrum (AA).The lead content of filtrating (mark with the 10g raw material is expressed) is 37.1ppm.
L2: will quantitatively be transferred to available from the resistates of the humidity on the filter paper of L1 in second 600ml beaker, and add 100ml water and 100ml concentrated nitric acid to it.Scheme afterwards is identical with L1's.Take out filtrating and be used for plumbous analyze (through atomic absorption spectrum), and find to contain 3.12ppm lead (mark with the 10g initial raw material is expressed).
L3: will quantitatively be transferred in the 3rd the 600ml beaker available from the resistates of the humidity of L2, and add 100ml water and 100ml concentrated nitric acid to it.Scheme afterwards is identical with L1's.Take out filtrating and be used for plumbous analyze (through atomic absorption spectrum), and find to contain 1.01ppm lead (mark with the 10g initial raw material is expressed).
L4: will quantitatively be transferred in the 4th the 600ml beaker available from the resistates of the humidity of L3, and add 100ml water and 100ml concentrated nitric acid to it.Scheme afterwards is identical with L1's.Take out filtrating and be used for plumbous analyze (through atomic absorption spectrum), and find to contain 0.65ppm lead (mark with the 10g initial raw material is expressed).
L5: will quantitatively be transferred in the 5th the 600ml beaker available from the resistates of the humidity of L4, and add 100ml water and 100ml concentrated nitric acid to it.Scheme afterwards is identical with L1's.Take out filtrating and be used for plumbous analyze (through atomic absorption spectrum), and find to contain 0.0ppm lead (mark with the 10g initial raw material is expressed).
The resistates that is obtained is designated as the final residual thing from raw material, in leach liquor, disengages the lead that is lower than 1ppm because find to utilize the nitric acid of ultrasonic agitation to leach continuous release for 2 times.This final residual thing is considered to not contain basically nitric acid dissoluble lead part.
In the experiment repeatedly of adopting identical desliming washing and exsiccant Playa material sample; Find that continuous 5 are utilized the nitric acid leaching step of ultrasonic agitation to be enough to produce the final residual thing---in each experiment, last 2 successive leach step and in leach liquor, disengage the lead that is lower than 1ppm.
Embodiment 2
Present embodiment has been explained and has been used for according to the present invention identifying and can removes the reagent of the insoluble part of nitric acid and the program of condition from the sample part at least.Sample is the Playa material of describing among the embodiment 1.The basis of program is at first from sample, strictly to remove nitric acid dissoluble lead part, in follow-up tentative leaching step, seeks plumbous appearance then.In the present embodiment, tentative leaching step relates in the aqueous acid condition and uses tin protochloride.
The final residual thing is by producing in washing of the 10g desliming described in embodiment 1 and the exsiccant Playa material.The final residual thing is transferred in the beaker of 600ml, and to wherein add to measure consumption by (a) 100ml water; (b) 100ml concentrated hydrochloric acid; (c) liquid of 8g stannous chloride dihydrate (dissolved) composition.Tin protochloride is a kind of known reductive agent.Place the Soniclean thermostatic ultrasonic to bathe in (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 1 hour, next stop 1 hour, opened then 1 hour, the rest may be inferred, makes the ultra sonic bath time add up to 8 hours.Use the slurry in No. 1 filter paper filtering beaker of Whatman, and take out filtrating and carry out plumbous analyze (sample being delivered to the Veolia laboratory of Adelaide, AUS) through ICP.The lead content of filtrating (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is 21ppm.This plumbous amount is apparently higher than at the final sum lead (being lower than 1ppm) that nitroxylic acid second from the bottom/the ultrasonic leaching step is found that is used for producing the final residual thing.In other words, the above-mentioned reductive acid that utilizes hydrochloric acid and tin protochloride leaches and causes and from the final residual thing, removed the insoluble plumbous part of nitric acid at least in part.In the case, the sign property level of the insoluble lead of nitric acid in desliming washing and the exsiccant Playa raw material (like preceding definition) is 21ppm.
The resistates that above-mentioned acid reduction is leached on the filter paper that obtains afterwards is transferred in the beaker of 600ml, and adds the aqueous sodium hydroxide solution of 200ml 4% to it.This beaker is placed ultra sonic bath, and in this ultra sonic bath, carried out the leaching scheme as previously mentioned 8 hours.After leaching/supersound process finishes,, and filtrating is carried out lead analysis through flame atomic absorption spectrometry through Whatman 1 filter paper filtering slurry.The lead content of filtrating (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is 6.5ppm.Can know from this result and to see that above-mentioned (a) is effective especially for from sample, removing the insoluble plumbous part of nitric acid in the order of leaching step under the sour reductive condition and (b) the leaching step under the alkali condition.
Caustic liquor leaches can not remove the insoluble plumbous part of nitric acid from the final residual thing that this type of raw material produced
To in aforesaid 4% aqueous sodium hydroxide solution, directly leach from the final residual thing of 10g desliming washing and exsiccant Playa material (preparation described in embodiment 1).After leaching/supersound process finishes,, and filtrating is carried out lead analysis through flame atomic absorption spectrometry through Whatman 1 filter paper filtering slurry.The lead content of filtrating (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is lower than 1ppm.This experiment shows, uses the part at least of the insoluble plumbous part of the aqueous sodium hydroxide solution leaching under ultrasonic agitation not causing nitric acid to remove.After the leaching step in the sour reductive condition before the appearance of the above-mentioned lead in alkali leaching liquor betides (referring to preceding text).This can be explained as follows: under acid/reduction leaching condition, the insoluble plumbous part of some nitric acid is converted into (leachability) the plumbous part that can be leached in the caustic liquor.
According to instruction of the present invention, the pre-treatment that above-mentioned (a) is suitable for supplying raw materials in the leaching step under the sour reductive condition and (b) order of the leaching step under the alkali condition, said pre-treatment can realize the subsequent recovery (referring to embodiment 3) of indissoluble gold.
Embodiment 3
How the be to use reagent and the condition (referring to embodiment 2) of removing the insoluble plumbous part of nitric acid at least in part that present embodiment shows can reclaim indissoluble gold.Reagent and condition comprise that (a) is in leaching step under the sour reductive condition and (b) the leaching step under the alkali condition.These two steps all comprise the use ultrasonic agitation.
10g desliming washing and exsiccant Playa material (described in the embodiment 1) are delivered to professional golden test experience chamber (Amdel) to be detected with the fire that carries out gold and confirms.The gold detected result is 0.3ppm.
Another sample to being made up of 10g desliming washing and exsiccant Playa material provides following pre-treatment (referring to embodiment 2): this sample transfer to the beaker of 600ml, and is comprised (a) 100ml water to interpolation wherein; (b) 100ml concentrated hydrochloric acid; (c) liquid of 8g stannous chloride dihydrate (dissolved).Place the Soniclean thermostatic ultrasonic to bathe in (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 1 hour, next stop 1 hour, opened then 1 hour, the rest may be inferred, makes the ultra sonic bath time add up to 8 hours.Use the slurry that is obtained in No. 1 filter paper filtering beaker of Whatman, this resistates is transferred in the beaker of a 600ml by filter paper, and to the aqueous sodium hydroxide solution that wherein adds 200ml 4%.This beaker is placed the Soniclean ultra sonic bath, and handle according to above-described ultra sonic bath scheme.Pointed like embodiment 2, the aforesaid combination of these steps has realized from raw material, at least partly removing the insoluble part of nitric acid.
Gold reclaims:
The slurry that uses Whatman 1 filter paper filtering to be obtained, and use following chloroazotic acid scheme to detect the gold content of resistates:
200ml concentrated hydrochloric acid and 50ml concentrated nitric acid are added in the 600ml beaker, and add resistates immediately.This beaker is put to ultra sonic bath (60 ℃) and stirred 2 minutes at 250W (full power).This beaker placed on the hot-plate and be heated to boil 5 minutes, and then be placed in the ultra sonic bath and 250W restir 2 minutes.This beaker is placed on the heating plate and reheat boiled 5 minutes to rising, and (for the third time) is placed in the ultra sonic bath and at 250W and stirred 2 minutes again then.Subsequently this beaker is put back to hot-plate and makes its boiling, until emitting of (a) nitrous fumes stop and (b) liquid volume in the beaker reduce to 80ml.This moment is through the slurry in the Whatman 1 filter paper heat filtering beaker, and reservation filtrating is to be used for the atomic absorption spectrochemical analysis of gold.Find that gold content (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is 7.0ppm.Compare with the golden detected value (0.3ppm) that detects discovery through the standard fire, can find out that method of the present invention provides the pre-treatment that can reclaim indissoluble gold, the recovery of said indissoluble gold obviously surpasses fiery detection level.
Embodiment 4
Present embodiment shows be with embodiment 2 in distinct reagent and the condition described how can be used for from specific sample, removing at least in part the insoluble plumbous part of nitric acid.Similar with embodiment 2, through at first from sample strictness remove nitric acid dissoluble lead part, in follow-up test property leaching step, seek plumbous appearance then and explore suitable reagent and condition.What present embodiment showed is 2 step test method(s)s, wherein, (a) uses first of ammoniacal liquor to leach the insoluble plumbous part of nitric acid is converted into the form (yet plumbous part is not disengaged to ammoniacal liquor) that can leach; And (b) use second of chloroazotic acid to leach and disengage the plumbous part of the leachability that in first leaches, forms.Twice leaching all utilizes ultrasonic agitation to carry out.
The final residual thing is by producing in washing of the 10g desliming described in embodiment 1 and the exsiccant Playa material.The final residual thing is transferred in the beaker of a 600ml, and adds the liquid that the ammoniacal liquor by 200ml 7.5% constitutes to it.Place the Soniclean thermostatic ultrasonic to bathe (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 10 minute, next stop 2 hours, opened then 10 minutes, the rest may be inferred, makes the ultra sonic bath time add up to 8.5 hours.Use the slurry in No. 1 filter paper filtering beaker of Whatman, and take out filtrating and carry out lead analysis through atomic absorption spectrum.The lead content of filtrating (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is 0.92ppm.This plumbous amount is not apparently higher than at the lead (being lower than 1ppm) that final sum penult nitric acid/the ultrasonic leaching step is found that is used for producing the final residual thing.
Use the chloroazotic acid scheme of describing in the above experiment 3 to handle the resistates that leaches available from above-mentioned ammonia, difference is, detects the plumbous rather than gold (chloroazotic acid has sizable molten plumbous ability, though lower than nitric acid) of final liquid.The discovery lead content is 10.23ppm (mark with 10g washing at first and exsiccant Playa raw material is expressed)---this is apparently higher than being used for producing the penult of final residual thing and the lead (being lower than 1ppm) that finally nitric acid/the ultrasonic leaching step is found.
This result shows that above-mentioned ammonia leaches step the insoluble plumbous part of the nitric acid in the resistates is converted into the plumbous part of leachability (leaching it through chloroazotic acid is partly removed at least).
According to instruction of the present invention, above-mentioned ammonia leach with use remove the plumbous part of leachability (in the ammonia leaching, forming) leaching combine the pre-treatment that is suitable for supplying raw materials, said pre-treatment can realize the subsequent recovery (referring to embodiment 5) of indissoluble gold.
Embodiment 5
What present embodiment showed is how can use ammonia to leach and subsequent another water-based leaching step process washing and exsiccant Playa raw material, and said another water-based leaches step and removes formed (can leach) lead in the deammoniation leaching.The insoluble plumbous part of nitric acid (referring to embodiment 4) is removed in this processing at least in part, and demonstration can be reclaimed indissoluble gold.
10g desliming washing and the thin Playa material of exsiccant are delivered to professional golden test experience chamber (Amdel) to be detected with the fire that carries out gold and confirms.The gold detected result is 0.3ppm (MV of double sample).
Another sample to being made up of 10g desliming washing and exsiccant Playa material provides following pre-treatment (referring to embodiment 4): in the beaker with sample transfer to a 600ml, and the liquid that constitutes by the ammoniacal liquor of 200ml 7.5% to its interpolation.Place the Soniclean thermostatic ultrasonic to bathe (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 10 minute, next stop 2 hours, opened then 10 minutes, the rest may be inferred, makes the ultra sonic bath time add up to 8.5 hours.Use the slurry in No. 1 filter paper filtering beaker of Whatman, and use the chloroazotic acid scheme of describing in the experiment 3 that resistates is carried out gold analysis.Find that gold content (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is 3.5ppm.Compare and can find out with the golden detected value (0.3ppm) that detects discovery through the standard fire, method of the present invention provides the pre-treatment that can reclaim indissoluble gold, and the recovery of said indissoluble gold obviously surpasses fiery detection level.
Embodiment 6
What present embodiment was explained is the use of the present invention for different original materials.Original material is called CH-4 by CANMET mining and mineral sciences laboratory (555 Booth St, Ottawa, Ontario, Canada).Sample characterizes as the part of " Canadian authentication reference material project (Canadian Certified Reference Materials Project) ".(Division Troilus, Chibougama Quebec) donated the raw material of CH-4 by Corporation Miniere Inmet in 2000.After pulverizing, grinding, screening and the mixing, yield is 37%.This material is the fine powder of order footpath less than 45 microns (325 orders).The host rock of raw material is inclined to one side plagioclasite (meta-anorthosite).Mineralogy comprises pyrrhotite, pyrite and yellow copper ore, and a spot of zink sulphide, lead glance and molybdenum glance.The average gold content of CH-4 CANMET standard is provided as 0.88ppm, and laboratory internal standard difference is 0.04ppm, and standard deviation is 0.04ppm between the laboratory.
Program is at first from CANMET sample CH-4, strictly to remove nitric acid dissoluble lead part, in follow-up tentative leaching step, seeks plumbous appearance then.In the present embodiment, tentative leaching step relates in the aqueous acid condition and uses tin protochloride.
Described in embodiment 1 by 10g CANMET CH-4 material production final residual thing.In the 4th and the 5th nitric acid leach liquor, not finding can detected lead.The final residual thing is transferred in the beaker of 600ml, and to wherein add to measure consumption by (a) 100ml water; (b) 100ml concentrated hydrochloric acid; (c) liquid of 8g stannous chloride dihydrate (dissolved) composition.Tin protochloride is a kind of known reductive agent.Place the Soniclean thermostatic ultrasonic to bathe in (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 1 hour, next stop 1 hour, opened then 1 hour, the rest may be inferred, makes the ultra sonic bath time add up to 8 hours.Use the slurry in No. 1 filter paper filtering beaker of Whatman, and take out filtrating and carry out plumbous analyze (sample being delivered to the Veolia laboratory of Adelaide, AUS) through ICP.The lead content of filtrating (mark with 10g CH-4 raw material is expressed) is 14ppm.This plumbous amount is apparently higher than at the lead (being lower than 1ppm) that final sum penult nitric acid/the ultrasonic leaching step is found that is used for producing the final residual thing.In other words, the above-mentioned reductinic acid that utilizes hydrochloric acid and tin protochloride leaches and causes and from the final residual thing, removed the insoluble plumbous part of nitric acid at least in part.In the case, the sign property level of the insoluble lead of nitric acid in desliming washing and the exsiccant Playa raw material (like preceding definition) is 14ppm.
The resistates that above-mentioned acid reduction is leached on the filter paper that obtains afterwards is transferred in the beaker of 600ml, and adds the aqueous sodium hydroxide solution of 200ml 4% to it.This beaker is placed ultra sonic bath, and in this ultra sonic bath, carried out the leaching scheme as previously mentioned 8 hours.After leaching/supersound process finishes,, and filtrating is carried out lead analysis through flame atomic absorption spectrometry through Whatman 1 filter paper filtering slurry.The lead content of filtrating (mark with initial washing of 10g and exsiccant Playa raw material is expressed) is 2.8ppm.Can know from this result and to see that above-mentioned (a) is effective especially for from sample, removing the insoluble plumbous part of nitric acid in the order of leaching step under the sour reductive condition and (b) the leaching step under the alkali condition.
Embodiment 7
Present embodiment is based on the research to CANMET sample CH-4.How the reagent (referring to embodiment 6) of removing the insoluble plumbous part of nitric acid at least in part that is to use that present embodiment shows can reclaim indissoluble gold.Through using sour reductive condition from raw material, to disengage indissoluble gold research.
Detect (referring to embodiment 6) based on conventional gold, the CH-4 material contains the gold of 0.88ppm.
Sample to being made up of 10g CANMET CH-4 material provides following pre-treatment: this sample transfer to the beaker of 600ml, and is comprised (a) 100ml water to wherein adding; (b) 100ml concentrated hydrochloric acid; (c) liquid of 8g stannous chloride dihydrate (dissolved).Place the Soniclean thermostatic ultrasonic to bathe (the 250W peak power is provided with, and bathes frequency 42kHz) in this beaker.The ultra sonic bath temperature is set to 60 ℃, and power setting is decided to be 60%, corresponding to the power of 150W.With ultrasonic power application 1 hour, next stop 1 hour, opened then 1 hour, the rest may be inferred, makes the ultra sonic bath time add up to 8 hours.Use the slurry that is obtained in No. 1 filter paper filtering beaker of Whatman, this resistates is transferred in the beaker of a 600ml by filter paper, and to the aqueous sodium hydroxide solution that wherein adds 200ml 4%.This beaker is placed the Soniclean ultra sonic bath, and handle according to above-described ultra sonic bath scheme.Pointed like embodiment 2, the aforesaid combination of these steps has realized from raw material, at least partly removing the insoluble part of nitric acid.
Gold reclaims:
The slurry that uses Whatman 1 filter paper filtering to be obtained, and use following chloroazotic acid scheme to detect the gold content of resistates:
200ml concentrated hydrochloric acid and 50ml concentrated nitric acid are added in the 600ml beaker, and add resistates immediately.This beaker is put to ultra sonic bath (60 ℃) and stirred 2 minutes at 250W (full power).This beaker placed on the hot-plate and be heated to boil 5 minutes, and then be placed in the ultra sonic bath and 250W restir 2 minutes.This beaker is placed on the hot-plate and reheat boiled 5 minutes to rising, and (for the third time) is placed in the ultra sonic bath and at 250W and stirred 2 minutes again then.Subsequently this beaker is put back to hot-plate and makes its boiling, until emitting of (a) nitrous fumes stop and (b) liquid volume in the beaker reduce to 80ml.This moment is through the slurry in the Whatman 1 filter paper heat filtering beaker, and reservation filtrating is to be used for the atomic absorption spectrochemical analysis of gold.Find that gold content (mark with the 10g raw material is expressed) is 3.0ppm.Compare with the golden detected value (0.88ppm) that detects discovery through the standard fire, can find out, (use acid reduction leaching condition) of the present invention method provides the pre-treatment that can reclaim indissoluble gold, and the recovery of said indissoluble gold obviously surpasses fiery detection level.

Claims (21)

1. one kind is reclaimed improving one's methods of indissoluble gold from material, and said method comprises handles said material to remove the insoluble plumbous part of nitric acid at least in part.
2. the method for claim 1, said method comprise handles said material the insoluble plumbous part of the said nitric acid of at least a portion be converted into the plumbous part of leachability and leach said material to remove the plumbous part of said leachability.
3. each described method as in the aforementioned claim, the process of wherein from contain gold copper-base alloy, removing the insoluble plumbous part of nitric acid at least in part comprise said reagent in containing gold copper-base alloy and being selected from the group of being made up of reductive agent, plumbous complexing agent and molten plumbous agent are contacted.
4. each described method as in the aforementioned claim, said method comprises said material is contacted with reductive agent.
5. method as claimed in claim 5; Wherein said reductive agent is selected from the group of being formed and comprised sulphite, sulfur-bearing reductive agent, oxalic acid and other organic reducing agents by chromium (II), tin (II), copper (I), titanium (II) and titanium (III) part; Be preferably selected from tin (II) part, more preferably the form of tin protochloride.
6. each described method as in the aforementioned claim, said method comprises the said gold copper-base alloy that contains is contacted with plumbous complexing agent.
7. method as claimed in claim 6, wherein said molten plumbous agent and complexing agent are selected from the group of being made up of carboxylic acid and salt, oxymuriate, perchlorate, alkali, muriate, silicofluoride, phenolsulfonate and peroxide stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate.
8. method as claimed in claim 7; Wherein, (a) said carboxylic acid is selected from the group of being made up of Hydrocerol A, lactic acid, acetate, formic acid, isopropylformic acid, Xaxa and salt thereof, and (b) said muriate is selected from the group of being made up of ammonium chloride, sodium-chlor, Repone K, calcium chloride and strontium chloride.
9. each described method as in the aforementioned claim, wherein said method of removing the insoluble plumbous part of nitric acid at least in part strengthens through at least one step that is selected from the group of being made up of following steps: (a) contain golden raw material and provide that violent stirring or cavitation stir, preferred ultrasonic agitation for said; (b) adopt the process of removing surface oxidation dirt layer at least in part; (c) at least 40 ℃, preferred at least 50 ℃ and more preferably at least 60 ℃ the temperature part at least of carrying out the insoluble part of nitric acid remove.
10. method as claimed in claim 9, wherein said method of removing the insoluble plumbous part of nitric acid at least in part strengthens through ultrasonic agitation.
11. a method that from the doubtful material that contains indissoluble gold, reclaims indissoluble gold, said method comprises: sample separation from said material; Said sample is carried out diagnostic to be leached; In final preparation of leaching resistates, leach the lead content of confirming filtrating by last two nitroxylic acids, and guarantee that in these two kinds of situations lead content is lower than 5ppm, preferably is lower than 1ppm; Said final leaching resistates is suitable for dissolving the processing of the insoluble plumbous part of nitric acid; To carry out plumbous analysis from the filtrating of treated final leaching resistates; Lead in the filtrating of wherein said treated final residual thing surpasses 1.5ppm; And said method also comprises to be used the method be suitable for dissolving the insoluble plumbous part of nitric acid to handle said material to exhaust the resistates of the insoluble plumbous part of nitric acid and from the said resistates that exhausts the insoluble plumbous part of nitric acid, reclaim gold with generation.
12. as each described method in the aforementioned claim, wherein said method of removing the insoluble lead of nitric acid at least in part is a hydrometallurgical process, said hydrometallurgical process produces the lead that surpasses 1.5ppm in filtrating when being applied to said final residual thing.
13. like each described method in the aforementioned claim, the step of wherein removing the nitric acid insolubles at least in part provides the comparison fire that material carries out to detect indicated higher gold recovery.
14. like each described method in the aforementioned claim, wherein said material comprises the non-silicon-dioxide obscurant that is retained in the said final residual thing, and comprises the insoluble plumbous part of said nitric acid.
15. as each described method in the aforementioned claim; The insoluble plumbous part of wherein said nitric acid transforms in leach liquor and during dissolving, usually with the semi-invariant that is lower than callable nitric acid dissoluble lead part in the continuous nitric acid of said material leaches 10%, as be lower than 5%, be lower than 2% and 1% the amount of being lower than exist.
16. like each described method in the aforementioned claim, the insoluble plumbous part of wherein said nitric acid comprises poor sulphur lead sulfate part.
17. like each described method in the aforementioned claim, wherein said material is selected from the group of being made up of Playa material and copper mine stone.
18. a system that from the material that comprises at least some indissoluble golds, reclaims gold, said system comprises:
(i) means that said material contacted with the reagent of the insoluble plumbous part of at least a portion nitric acid that is suitable for transforming said material and
(ii) said material is contacted with leaching agent removing the means of the plumbous part of leachability,
(iii) handle said material to disengage the means of the gold that comprises indissoluble gold.
19. system as claimed in claim 16, wherein said step reagent (ii) is selected from by reductive agent, plumbous complexing agent, the group of dissolving plumbous agent and forming.
20. like claim 16 or 17 described systems, said system also is included in the means of step (i) heat application or ultrasonic energy to arbitrary step (iii).
21. as each described method in the aforementioned claim, its with this paper in the reference implementation example any one describe similar basically.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111411240A (en) * 2020-04-23 2020-07-14 贺利氏贵金属技术(中国)有限公司 Method for recovering noble metal from waste catalyst containing noble metal

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2766812A1 (en) * 2009-07-01 2011-01-06 Precious Metals Recovery Pty Ltd Smelting method
IN2014KN01462A (en) 2011-12-15 2015-10-23 Advanced Tech Materials
DK3041964T3 (en) 2013-09-04 2023-02-20 Mining and Process Solutions Pty Ltd PROCEDURE FOR EXTRACTION OF COPPER AND/OR PRECIOUS METAL
US20160319444A1 (en) 2013-12-20 2016-11-03 Greene Lyon Group, Inc. Method and apparatus for recovery of noble metals, including recovery of noble metals from plated and/or filled scrap
JP2017506702A (en) * 2014-02-26 2017-03-09 グリーン リヨン グループ, インコーポレーテッドGreene Lyon Group, Inc. Recovery of gold and / or silver from scrap
WO2016210051A1 (en) 2015-06-24 2016-12-29 Greene Lyon Group, Inc. Selective removal of noble metals using acidic fluids, including fluids containing nitrate ions
MX2016014770A (en) 2014-05-12 2017-05-25 Summit Mining Int Inc Brine leaching process for recovering valuable metals from oxide materials.
US20150329934A1 (en) * 2014-05-15 2015-11-19 Rulon W. Dahl Dahl Process
CN104263939A (en) * 2014-09-09 2015-01-07 中国电器科学研究院有限公司 Method for recovering rare/inert metals from bottom electroplating copper/nickel material
EP3286346A4 (en) 2015-04-21 2019-01-16 University of Saskatchewan Methods for selective leaching and extraction of precious metals in organic solvents
CN105907985B (en) * 2016-06-29 2017-10-24 贵州银花妆开发有限公司 Gold and the method purified are extracted in a kind of gold mine
CA3008880A1 (en) * 2017-06-22 2018-12-22 Lifezone Limited Hydrometallurgical treatment process for extraction of precious, base and rare elements
US10526682B2 (en) * 2017-07-17 2020-01-07 Enviroleach Technologies Inc. Methods, materials and techniques for precious metal recovery
US11040898B2 (en) 2018-06-05 2021-06-22 The Regents Of The University Of California Buffer-free process cycle for CO2 sequestration and carbonate production from brine waste streams with high salinity
AU2020223864B2 (en) * 2019-02-22 2022-08-18 Gebrüder Dorfner GmbH & Co. Kaolin- und Kristallquarzsand-Werke KG Method for producing solid particles, solid particles, and the use thereof
WO2021061184A1 (en) * 2019-09-23 2021-04-01 All Green Recycling, Inc. Systems and methods of efficiently recovering precious metals using an alkaline leach, ultrasound, and electrolysis
CN110643827B (en) * 2019-10-22 2022-02-18 贵州大学 Green method for dissolving and extracting gold element
CN111579338A (en) * 2020-06-28 2020-08-25 长春黄金研究院有限公司 Method for measuring gold in secondary utilization waste
CN113151667B (en) * 2021-04-19 2022-10-14 上海第二工业大学 Method for recycling rare and precious metal elements from waste LED packaging
CA3235332A1 (en) 2021-10-18 2023-04-27 The Regents Of The University Of California Seawater electrolysis enables mg(oh)2 production and co2 mineralization
CN114807623B (en) * 2022-03-10 2023-09-22 金川集团股份有限公司 Method for removing tellurium from copper anode slime leaching residues
CN115112518B (en) * 2022-07-04 2023-09-12 山东招金金银精炼有限公司 Analysis method for gold content in electroforming cylinder liquid

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4229270A (en) * 1978-04-12 1980-10-21 The International Nickel Co., Inc. Process for the recovery of metal values from anode slimes
US4374098A (en) * 1981-06-22 1983-02-15 Sumitomo Metal Mining Co., Ltd. Method of concentrating silver from anode slime
CN1163314A (en) * 1996-11-21 1997-10-29 招远市北截金矿 Technical process for extracting valuable metal from gold slime
CN1199780A (en) * 1997-05-15 1998-11-25 昆明贵金属研究所 Ag and Au extracting and Sb, Bi, Cu and Pb recovering process from lead slime
US5958257A (en) * 1997-01-07 1999-09-28 Gerber Plumbing Fixtures Corp. Process for treating brass components to reduce leachable lead
JP2003089827A (en) * 2001-09-14 2003-03-28 Nippon Mining & Metals Co Ltd Method for refining silver

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856507A (en) * 1973-03-12 1974-12-24 Owens Illinois Inc Recovery of gold from solution in aqua regia
US4094668A (en) * 1977-05-19 1978-06-13 Newmont Exploration Limited Treatment of copper refinery slimes
US4295881A (en) * 1979-04-23 1981-10-20 Texasgulf Inc. Process for extraction of platinum group metals from chromite-bearing ore
US4375984A (en) * 1980-08-14 1983-03-08 Bahl Surinder K Recovery of gold from bromide etchants
ZA82479B (en) * 1981-02-05 1983-04-27 Johnson Matthey Plc Recovery of precious metals
CA1198080A (en) * 1981-04-15 1985-12-17 Freeport Minerals Company Simultaneous leaching and electrodeposition of precious metals
US4662938A (en) * 1984-10-11 1987-05-05 Whitney John W Recovery of silver and gold
US4931415A (en) * 1986-08-20 1990-06-05 Ferro Corporation Metal melting crucible
US5013359A (en) * 1988-10-31 1991-05-07 Hydrochem Developments Ltd. Process for recovering gold from refractory sulfidic ores
CN1095422A (en) * 1993-05-20 1994-11-23 薛光 The full wet method gold and silver of gold mud separating technology
US5425800A (en) * 1993-10-26 1995-06-20 Fmc Corporation Recovery of precious metal values from refractory ores
US5667557A (en) * 1994-03-25 1997-09-16 E. I. Du Pont De Nemours And Company Hydrometallurgical extraction and recovery of copper, gold, and silver via cyanidation and electrowinning
US5411575A (en) * 1994-03-25 1995-05-02 E. I. Du Pont De Nemours And Company Hydrometallurgical extraction process
CA2147307A1 (en) * 1994-04-20 1995-10-21 Dean Butler Noble metal recovery
US5622615A (en) * 1996-01-04 1997-04-22 The University Of British Columbia Process for electrowinning of copper matte
US5961833A (en) * 1997-06-09 1999-10-05 Hw Process Technologies, Inc. Method for separating and isolating gold from copper in a gold processing system
CA2293691C (en) * 1997-06-09 2006-11-07 Hw Process Technologies, Inc. Method for separating and isolating precious metals from non precious metals dissolved in solutions
DE19880534C2 (en) * 1997-06-16 2002-10-10 Mitsubishi Materials Corp Process for cleaning precious metals
AU2001257646A1 (en) * 2000-04-28 2001-11-12 Mintek Gold recovery process
GB2370567B (en) * 2000-11-01 2005-05-04 Lee Fisher Robinson Extraction processes
US6500231B1 (en) * 2001-03-29 2002-12-31 Newmont Usa Limited Recovery of precious metals from thiosulfate solutions
CN101139660A (en) * 2007-10-08 2008-03-12 郑满秀 Method for extracting iron-lead and gold-silver from gold concentrate acidifying baking residue

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4229270A (en) * 1978-04-12 1980-10-21 The International Nickel Co., Inc. Process for the recovery of metal values from anode slimes
US4374098A (en) * 1981-06-22 1983-02-15 Sumitomo Metal Mining Co., Ltd. Method of concentrating silver from anode slime
CN1163314A (en) * 1996-11-21 1997-10-29 招远市北截金矿 Technical process for extracting valuable metal from gold slime
US5958257A (en) * 1997-01-07 1999-09-28 Gerber Plumbing Fixtures Corp. Process for treating brass components to reduce leachable lead
CN1199780A (en) * 1997-05-15 1998-11-25 昆明贵金属研究所 Ag and Au extracting and Sb, Bi, Cu and Pb recovering process from lead slime
JP2003089827A (en) * 2001-09-14 2003-03-28 Nippon Mining & Metals Co Ltd Method for refining silver

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111411240A (en) * 2020-04-23 2020-07-14 贺利氏贵金属技术(中国)有限公司 Method for recovering noble metal from waste catalyst containing noble metal

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