CN103789546A - Method for gold leaching method by thiourea - Google Patents
Method for gold leaching method by thiourea Download PDFInfo
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- CN103789546A CN103789546A CN201410042871.XA CN201410042871A CN103789546A CN 103789546 A CN103789546 A CN 103789546A CN 201410042871 A CN201410042871 A CN 201410042871A CN 103789546 A CN103789546 A CN 103789546A
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- China
- Prior art keywords
- gold
- leaching
- thiourea
- acid
- thiocarbamide
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 208
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 125
- 239000010931 gold Substances 0.000 title claims abstract description 125
- 238000002386 leaching Methods 0.000 title claims abstract description 89
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 38
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims description 12
- 229910001447 ferric ion Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 6
- -1 bio-oxidation Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910052964 arsenopyrite Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 239000000920 calcium hydroxide Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000292 calcium oxide Substances 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 239000004576 sand Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 240000006409 Acacia auriculiformis Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for gold leaching by thiourea. When the gold is leached by an acid thiourea solution, aiming at the different gold-containing mine resources, such as the oxidized ore, and the ore pulp or the roasted sand which is obtained after by the hardy-leached sulphide ore is pretreated (oxidized under oxygen pressure, biologically oxidized or roasted) by means of oxidation, the acid degree of the ore pulp is controlled at the pH which is more than 2.2 and is less than or equal to 3.5. The ion concentration of the ferric iron is controlled by adjusting and controlling the acid degree and the alkali degree of the solution, so that the consumption of the acid can be obviously reduced; compared with a cyaniding gold leaching system, the method disclosed by the invention has the advantages that the use amount of the alkali (such as calcium oxide or calcium hydroxide) can be obviously reduced; when the oxidized gold ore is leached, compared with the common thiourea leaching condition (pH is 1-2), the consumption of the acid can be obviously reduced. Under the gold leaching condition, not only can the use amount of the acid and the alkali be reduced, but also the ion concentration of the ferric iron can be more economically and effectively controlled, the thiourea consumption can be reduced, and the leaching dynamics and the leaching recovery rate of the gold can be guaranteed.
Description
Technical field
The invention belongs to the nuisanceless technical field that extracts gold from of non-cyaniding, relate to and a kind ofly can economical, effectively reduce the golden method of soaking of thiocarbamide consumption.
Background technology
Gold is one of important precious metal, at occurring in nature, it with metallic state high dispersing in the earth's crust.Due to special physics and chemistry character, gold, except for jewellery, finance deposit, is also widely used in fields such as electronics, computer, precision instrument, Aeronautics and Astronautics.
At present, gold industry generally adopts cyanidation technique to extract gold from from mineral, because this technology is relatively simple, effective and economical.Because prussiate toxicity is very high, adult's lethal quantity is only 50 milligrams, therefore, uses prussiate to cause the worry of people to environment aspect.At present, some countries and regions have banned use of prussiate; It is relatively slow that cyanidation technique is carried golden process kinetics, generally needs 24 hours or the longer time; Along with the exhaustion that gold mine is easily soaked on earth's surface, the primary ore of discovery mostly is sulphide ores.To these, containing gold mine, cyaniding effect is bad, causes that cyanide consumption is too high or golden leaching rate is very low, or both have concurrently.In order to improve the golden rate of recovery, development and application of gold industry oxidation pre-treatment technology, as chemical oxidation, oxygen are pressed (or autoclave) oxidation, bio-oxidation and roasting (due to environmental problem, the application of roasting technology is restricted) etc.But the ore pulp producing after oxidation pre-treatment or calcining have peracid to form more, if cyanide gold-leaching need to consume suitable alkali (lime etc.) and neutralize, cause gold smelting cost to improve.
In order to overcome above problem, chemist and metallurgist paid a large amount of effort seek the nuisanceless acidity of non-cyaniding soak gold reagent with replace prussiate, wherein, thiocarbamide is considered to most promising reagent, because its is almost non-toxic, be applicable to acidic solution, to soak golden power fast again, be the 5-10 of prussiate gold leaching-out speed doubly.
Find after deliberation, in Gold Leaching In Thiourea Solutions system, ferric ion (Fe (III)) be the most economical, effectively soak golden oxygenant very fast because thiocarbamide/Fe (III) system is soaked golden speed; Fe (III) can get it on the spot, and does not need another reagent adding; The advantages such as it is generally acknowledged in sulfate system, thiocarbamide and sulfate radical and Fe (III) can form stable complex compound, and thiocarbamide is slower by Fe (III) oxygenolysis, and thiocarbamide consumption is lower.But, in the time that practical application thiocarbamide-ferric iron (Fe (III)) acidic solution (pH is conventionally between 1-2) soaks gold, thiocarbamide consumption and golden leaching yield alter a great deal with the difference of leaching operational condition and mineralogical property, conventionally compared with cyanidation technique, thiocarbamide and to control the higher and golden leaching yield of the reagent consuming cost of current potential lower.For this reason, the application of Gold Leaching In Thiourea Solutions technology is very limited.
In order to reduce thiocarbamide consumption, people once adopted many kinds of measures and method control leaching system current potential or eliminate too much ferric iron and realize, as before in thiocarbamide leaching with dilution heat of sulfuric acid wash in advance, add complexing agent stabilizing trivalent iron reducing its activity, (the sulfurous gas SO that adds reductive agent
2, S-WAT Na
2sO
3, V-Brite B Na
2s
2o
4deng) ferric ion is reduced into ferrous ion etc.These measures are all controlled significantly leaching current potential or are reduced iron (III) ionic concn, lowered thiocarbamide consumption, and security deposit's leaching velocity and leaching yield, but running cost is too high and the phenomenon such as not easy to operate, and above method is hard to carry on.With the research of Gold Leaching In Thiourea Solutions, oneself has a lot, respectively has quality.In patent CN88102653.0 " Technology for industrial extracting gold by thiocarbamide-iron leaching process ", extract material granularity is required to be-320 orders, and extraction time needs 32-40 hour, broken length consuming time, and cost is high, and leaching cycle is oversize; The advantages such as patent CN92105962.0 " extracts the method for gold and silver " with thiocarbamide have leaching yield high, with short production cycle, but in its leaching process, need to add containing SO
2industrial smoke, pollute production environment, and be unfavorable for manual operation; Patent CN200310110091.6 " bio-oxidation-thiourea resin pulp process gold extraction technology of refractory gold concentrate " loaded down with trivial details, the consuming time length of pretreatment technology; Patent CN200810136957.3 " a kind of gold-extracting process by thiourea carbon-in-pulp " has the advantages such as the rate of recovery is high, environmental protection.But above patent does not all provide in leaching process, how to control Leaching potential or Fe(III) technical problem such as concentration and thiocarbamide consumption.
In leaching process, there is thiocarbamide exorbitant expenditure and control Fe(III in existing Gold Leaching In Thiourea Solutions technology) concentration method deficiency, need a kind of Gold Leaching In Thiourea Solutions method that can economic, effectively reduce thiocarbamide consumption badly.Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method of economy, efficient Gold Leaching In Thiourea Solutions is provided, control ferric ion concentration or leaching current potential by regulating the potential of hydrogen of gold leaching solution, guarantee the significantly consumption of reduction thiocarbamide in the dynamic (dynamical) situation of molten gold, and can improve the method for the Gold Leaching In Thiourea Solutions of the golden rate of recovery.
In order to obtain method of the present invention, the present patent application people is by showing Gold Leaching In Thiourea Solutions system theoretical analysis, in the time that application thiocarbamide-Fe (III) system is carried gold from mineral, the dissolving Fe(III that need to consume of gold) ionic weight is low-down, as contained 10 grams of gold in mineral per ton, only need to consume the Fe (III) of 2.84 grams.But soak in golden process actual, for golden dissolving need to maintain the certain oxidizing potential of gold leaching solution or certain Fe(III) concentration.In addition, study discovery through the inventor, in simple solution, thiocarbamide is respectively first order reaction with thiocarbamide and Fe (III) concentration respectively by the speed of Fe (III) oxygenolysis.If Fe(III) too much, will cause a large amount of decomposition of thiocarbamide or thiocarbamide exorbitant expenditure.Therefore, how to control Fe (III) soaking the necessity in golden system, suitable concentration can be guaranteed again to soak golden speed, is one of this system most critical technology of reducing thiocarbamide.
When Gold Leaching In Thiourea Solutions, ferric ion is as oxygenant, and ore pulp acidity or pH value are generally controlled between pH1-2 in the prior art, and this is that Fe (III) ion produces precipitation in the time of pH2.2 because according to solution chemistry.When pH value is higher than 2.2 time, the activity (a of Fe (III)
fe (III)) there is following relation with pH:
log a
Fe(III)=3.417-3pH (1)
Can calculate the activity of Fe (III) in different pH values according to (1) formula.If compared with under low condition, the activity quotient of Fe (III) counts 1.0 in dilute solution or ionic strength, as calculated pH be 2.3,2.5,3.0,3.5 o'clock Fe (III) concentration of ordinary dissolution as follows respectively:
Above the thermodynamics calculation results shows, in simple aqueous in the time of pH>2.2, the concentration of free ferric ion is too low and can not meet and soak golden requirement.But at the thiocarbamide-Fe(III of sulfate medium) soak in golden system, ferric ion and sulfate ion and thiocarbamide molecule or separately and thiocarbamide molecule can form stable complex compound:
Fe
3++SO
4 2-+SC(NH
2)
2=[FeSO
4SC(NH
2)
2]
+
β
mix=4.26 × 10
6(2) and
Fe
3++SC(NH
2)
2=[FeSC(NH
2)]
3+
β
1=1.58×10
2
(3)
Fe
3++2SC(NH
2)
2=[Fe(SC(NH
2)
2)
2]
3+
β
2=2.75×10
8
(4)
Suppose and complex reaction (2), [SO only occur soaking in golden system
4 2-]=0.1 mole, [SC (NH
2)
2]=0.03 mole counts 1.0 with the activity quotient of various solutes, in the situation that pH value is greater than 2.2, and according to thermodynamic data rough calculation, concentration of ordinary dissolution or the [FeSO of Fe in gold leaching solution (III)
4(SC (NH
2)
2)]
+complexing ion concentration and pH have following relation:
log a
[FeSO4SC(NH2)2] +=log[[FeSO4（SC(NH
2)
2）]
+]=7.547-3pH
(5)
In different pH values, calculate according to (5) formula with throw out Fe (OH)
3complexing ion [the FeSO of balance
4(SC (NH
2)
2)]
+concentration (supposition activity quotient be 1.0) as follows:
Can find out from above-mentioned preliminary the thermodynamics calculation results, with throw out Fe (OH)
3the solubleness of the Fe (III) of balance in vitriol (0.1 mole of sulfate radical)-thiocarbamide (0.03 mole or 2.19 grams per liters) solution is very high, for example, is 1.114 mol/L at pH2.5, is 0.035 mol/L in the time of pH3.0.Through test determination, if in pH value higher than 2.3 in the situation that, ([FeSO
4(SC (NH
2)
2)]
+, i.e. (Fe
3+, SO
4 2-, SC (NH
2)
2between complex compound) Eo+ that forms of complexing ion is enough to dissolve element gold, so, controlling Fe (III) by solution chemistry control pH value is feasible at Fe (III) concentration or the oxidizing potential that soak in golden system.
The object of the invention is to complete by the following technical programs, specific operation process is as follows:
(1) gold mine raw material is carried out to the acid ore pulp forming after oxide treatment, add alkali neutralization precipitation ferric ion, by the acidity control of ore pulp and be stabilized in 2.2<pH≤3.5;
(2) Gold Leaching In Thiourea Solutions: add thiocarbamide to soak gold in ore pulp, soaking in golden process, by adding alkali or acid-conditioning solution pH value is controlled and is stabilized between 2.2<pH≤3.5.
Gold mine raw material of the present invention is sulfuration gold mine, oxidation gold mine, and wherein, sulfuration gold mine is primary ore or concentrate, comprises pyrite, pyrrhotite, arsenopyrite or mispickel.
In described gold mine raw material, for example, have acid-soluble ferric oxide to exist as (being oxidized gold mine) in mineral resources, directly acid adding is dissolved as oxygenant it; If be not with or without the oxide compound of enough acid-solubility three-irons, in thiourea solution, add sulfuric acid high (trivalent) iron and make oxygenant, sulfuric acid high (trivalent) concentration of iron is 0.2-0.5 grams per liter or 0.6-1.5 kg/tonne of ore deposit.
Described to sulfuration gold mine feed oxygen treatment technology, comprise Oxidation under pressurized oxygen, bio-oxidation, chemical oxidation or roasting.
Described gold mine raw material is oxidized in ore pulp after treatment, (calcium sulfate, the ironic hydroxide etc. that form when adding calcium oxide neutralization when sulfur acid, ferric sulfate and alkaline earth metal sulphate etc. are too high, whether have a significant effect as basis for estimation to pulp viscosity or to Gold Leaching In Thiourea Solutions), need carry out after solid-liquid separation, filter cake carries out Gold Leaching In Thiourea Solutions again.
The preferred lime powder of described alkali or milk of lime.
Described Gold Leaching In Thiourea Solutions, preferably thiourea concentration 1-4 grams per liter, preferred solid-to-liquid ratio 1:2.5-4.0, preferred leaching time are 2-6 hour.
Described leaching is carried out at 10-25 ℃.
In prior art, cause the consumption of thiocarbamide to have many reasons, but the inventor's research is found, the oxygenolysis thiocarbamide of ferric ion is main factor, other factors is if the oxidation of oxygen in the impact of the thermal destruction of mineral grain surface adsorption, thiocarbamide self, plain metal ion (except copper (II)), air etc. is on thiocarbamide consumption impact, very micro-as a rule.
Main innovation part of the present invention is: soak in golden system at thiocarbamide/Fe (III), in normal operations situation (thiocarbamide 1-4 grams per liter), control ferric ion concentration in gold leaching solution by the potential of hydrogen that regulates gold leaching solution, can guarantee to soak golden kinetics and can improve again the golden rate of recovery (because the meeting passivation of thiocarbamide degradation production or part passivation gold grain surface), what is more important can significantly lower thiocarbamide consumption.
Method of the present invention, there are solid theoretical basis and outstanding actual effect, by the method for regulator solution potential of hydrogen, economical, effectively control Fe (III) ionic concn or oxidizing potential, reduce significantly thiocarbamide consumption, for the widespread use of Gold Leaching In Thiourea Solutions system provides assurance.
Compared with prior art, the invention has the advantages that:
(1) soak gold mine slurry or solution acid alkalinity by adjusting, realize and control in solution ferric ion concentration or soak golden current potential, economical, reduce thiocarbamide consumption efficiently;
(2) in significantly reducing thiocarbamide consumption, can guarantee to soak golden kinetics, can improve again the golden rate of recovery, because can avoid the phenomenon on the part or all of passivation gold grain of thiocarbamide oxygenolysis product surface, this all leaches to make solubility auri;
(3) the acid ore pulp after preoxidation for sulphide ores, adopts the low acid of thiocarbamide/Fe (III) (or high pH value >2.2) to soak golden system, soak golden system with cyaniding alkalescence compared with, reduced the consumption of alkali (lime);
(4), for oxidation gold mine, compared with traditional Gold Leaching In Thiourea Solutions operational condition (pH1-2), obviously reduced reagent (acid) consumption.
Embodiment
With embodiment, the invention will be further described below, but the present invention is not limited to these embodiment.
Embodiment 1:
Adopt preparation thiocarbamide/Fe (III) solution in the molten golden speed of different pH pH-value determination pHs: to add reactive tank (iron-holder is as 3.0 grams) take the form of hydration ferric sulphate, and add water 800 milliliters and dissolve ferric sulphate; Add milk of lime regulator solution pH value 2.2,2.3,2.5,2.6,2.7,2.8,3.0,3.2,3.5, more all add thiocarbamide (4 grams) and water to 1 liter, adopt rotating-disk technology (400 revs/min of rotating speeds) at 25 ℃, to measure respectively golden dissolution rate.Result shows, as pH value of solution < 2.6, the dissolution rate of gold is very fast, with in pH≤2.2 o'clock quite; In the time of pH value >=2.7, the dissolution rate of gold increases and reduces with pH value, until between pH value 3.2-3.5.But in pH >=2.3 o'clock, thiocarbamide decomposition and consumption raises with pH value and obviously reduces.Between pH2.8-3.2, thiocarbamide consumption, compared with when the < pH2.2, has reduced more than 90%.
Embodiment 2:
Adopt preparation thiocarbamide/Fe (III) solution to measure molten golden speed under different Fe (III) concentration conditions: to prepare respectively Fe (III) concentration 0.2 and 0.5 grams per liter gold leaching solution, measure golden leaching rate (other condition is with embodiment 1) in pH value 2.5.Measurement result shows, the leaching rate and Fe(III of gold) ionic concn is that 3 grams per liters are identical, illustrates that, under this system and condition, iron concentration does not affect substantially on golden dissolution rate.
Embodiment 3:
Adopting preparation thiocarbamide/Fe (III) solution under different thiourea concentration conditions, to measure molten golden speed: to prepare respectively thiourea concentration 1.0,2.0,3.0 and 4.0 grams per liter gold leaching solutions, at pH value 2.5 and Fe(III) original concentration is under 1.0 grams per liter conditions, to measure golden leaching rate (other condition is with embodiment 1).Measurement result demonstration, the leaching rate of gold reduces with the reduction of thiourea concentration, and this speed and thiourea concentration are first order reaction, and in the time that thiocarbamide is 1 grams per liter, the leaching of gold is also obvious.
Embodiment 4:
Adopting preparation thiocarbamide/Fe (III) solution under condition of different temperatures, to measure molten golden speed: secure ph 2.6, thiourea concentration 4.0 grams per liters and Fe(III) original concentration concentration is 1.0 grams per liter gold leaching solutions, is respectively and under 10,15,20,25,30 ℃ of conditions, measures golden leaching rate (other condition is with embodiment 1) in temperature.Measurement result demonstration, the leaching rate of gold is subject to gold surface Control of chemical reaction, and the impact of temperature is comparatively remarkable.Be embodied under these conditions, when temperature during in 15-30oC the leaching rate of gold very fast; When temperature is during lower than 10oC, the leaching rate of gold is very slow.
Embodiment 5:
Oxidation gold mine soaks gold test: get 300 grams, oxidation sample ore and 800 ml water slurrying containing 4.6 grams/ton of gold, about adding 0.5 gram of high ferro (Fe (III), with the form of hydration ferric sulphate) and sulfuric acid and regulating ore pulp acidity and be stabilized in pH2.75; Adding thiocarbamide (3.6 grams) and water is 900 milliliters to total liquor capacity again, and leaching solid-to-liquid ratio is 1:3.0, and thiourea concentration is 4 grams per liters, and by regulating ore pulp acidity control pH value to leach in 2.8 left and right.Leaching 23 ℃ and stir under carry out, leaching time 4 hours, gold leaching rate 91.0%, thiocarbamide decomposition and consumption is 1.20 kgs/tonne of ore deposits.
Embodiment 6:
The impact that solid-to-liquid ratio consumes soaking gold and thiocarbamide:
Difficulty is soaked sulfuration gold mine (primary ore) and after Oxidation under pressurized oxygen pre-treatment, is soaked gold test: sulfuration raw gold ore (5.1 grams/ton of gold grades, element sulfur content 7.8) is first pressed preoxidation, oxidation ratio～98% of sulphur through oxygen.Its slurry filtration, gets the filter cake slurrying that adds water, and adds milk of lime slurry pH is modulated to 2.5 left and right; Add again thiocarbamide, add alkali simultaneously and make pH value rise to 2.8 left and right to carry out Leaching of Gold.Leaching is carried out under solid-to-liquid ratio 1:3.0, thiourea concentration 3 grams per liters, 22 ℃ and agitation condition.Leach 88.0%, 3 hour gold leaching rate of 2 hours gold leaching rates and reach 95.0%, thiocarbamide consumes 1.1 kgs/tonne of ore deposits.
Embodiment 7:
The impact that solid-to-liquid ratio consumes soaking gold and thiocarbamide:
Difficulty is soaked sulfuration gold mine (primary ore) and after Oxidation under pressurized oxygen pre-treatment, is soaked gold test: sulfuration raw gold ore (5.1 grams/ton of gold grades, element sulfur content 7.8) is first pressed preoxidation, oxidation ratio～98% of sulphur through oxygen.Its slurry filtration, gets the filter cake slurrying that adds water, and adds milk of lime slurry pH is modulated to 2.5 left and right; Add again thiocarbamide, add alkali simultaneously and make pH value rise to 2.8 left and right to carry out Leaching of Gold.Leaching is carried out under solid-to-liquid ratio 1:2.5, thiourea concentration 3 grams per liters, 22 ℃ and agitation condition.Leach 85.6%, 3 hour gold leaching rate of 3 hours gold leaching rates and reach 93.6%, thiocarbamide consumes 1.02 kgs/tonne of ore deposits.
Embodiment 8:
The impact that solid-to-liquid ratio consumes soaking gold and thiocarbamide:
Difficulty is soaked sulfuration gold mine (primary ore) and after Oxidation under pressurized oxygen pre-treatment, is soaked gold test: sulfuration raw gold ore (5.1 grams/ton of gold grades, element sulfur content 7.8) is first pressed preoxidation, oxidation ratio～98% of sulphur through oxygen.Its slurry filtration, gets the filter cake slurrying that adds water, and adds milk of lime slurry pH is modulated to 2.5 left and right; Add again thiocarbamide, add alkali simultaneously and make pH value rise to 2.8 left and right to carry out Leaching of Gold.Leaching is carried out under solid-to-liquid ratio 1:4.0, thiourea concentration 3 grams per liters, 22 ℃ and agitation condition.Leach 91.0%, 3 hour gold leaching rate of 3 hours gold leaching rates and reach 96.8%, thiocarbamide consumes 1.22 kgs/tonne of ore deposits.
Claims (8)
1. a method for Gold Leaching In Thiourea Solutions, is characterized in that specifically comprising the following steps:
(1) gold mine raw material is carried out to the acid ore pulp forming after oxide treatment, add alkali neutralization precipitation ferric ion, by the acidity control of ore pulp and be stabilized in 2.2<pH≤3.5;
(2) Gold Leaching In Thiourea Solutions: add thiocarbamide to soak gold in ore pulp, soaking in golden process, by adding alkali or acid-conditioning solution pH value is controlled and is stabilized between 2.2<pH≤3.5.
2. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, is characterized in that: the gold mine raw material of telling is sulfuration gold mine, oxidation gold mine, and wherein, sulfuration gold mine is primary ore or concentrate, comprises pyrite, pyrrhotite, arsenopyrite or mispickel.
3. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, is characterized in that: in described gold mine raw material, as there being acid-soluble ferric oxide to exist in mineral resources, directly acid adding is dissolved as oxygenant it; If be not with or without the oxide compound of enough acid-solubility three-irons, in thiourea solution, add ferric sulphate and make oxygenant, ferric iron concentration is 0.2-0.5 grams per liter or 0.6-1.5 kg/tonne of ore deposit.
4. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, is characterized in that: described gold mine raw material oxidation technology, comprises Oxidation under pressurized oxygen, bio-oxidation, chemical oxidation or roasting.
5. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, it is characterized in that: described gold mine raw material is oxidized in ore pulp after treatment, when sulfur acid, ferric sulfate and alkaline earth metal sulphate etc. are too high, need carry out after solid-liquid separation, filter cake carries out Gold Leaching In Thiourea Solutions again.
6. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, is characterized in that: the thiourea concentration 1-4 grams per liter of described Gold Leaching In Thiourea Solutions.
7. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, is characterized in that: the solid-to-liquid ratio 1:2.5-4.0 of described Gold Leaching In Thiourea Solutions.
8. the method for a kind of Gold Leaching In Thiourea Solutions according to claim 1, is characterized in that: described leaching is carried out at 10-25 ℃.
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| CN104531988A (en) * | 2014-12-26 | 2015-04-22 | 昆明冶金研究院 | Recovery process of complex multi-metal ores difficult to treat |
| US11884993B2 (en) | 2015-04-17 | 2024-01-30 | Jetti Resources, Llc | Process for leaching metal sulfides with reagents having thiocarbonyl functional groups |
| US11859263B2 (en) | 2016-10-19 | 2024-01-02 | Jetti Resources, Llc | Process for leaching metal sulfides with reagents having thiocarbonyl functional groups |
| CN107586953A (en) * | 2017-08-25 | 2018-01-16 | 金川集团股份有限公司 | A kind of method of concentration of precious metal |
| CN107586953B (en) * | 2017-08-25 | 2019-04-26 | 金川集团股份有限公司 | A kind of method of concentration of precious metal |
| CN108486367A (en) * | 2018-03-30 | 2018-09-04 | 陕西科技大学 | A method of using thiocarbamide assisting ultrasonic-Fenton Combined Treatment containing golden tailing |
| CN108842065A (en) * | 2018-05-31 | 2018-11-20 | 西北矿冶研究院 | Combined leaching agent for high-sulfur silver minerals and preparation method thereof |
| CN108842065B (en) * | 2018-05-31 | 2020-10-30 | 西北矿冶研究院 | Combined leaching agent for high-sulfur silver minerals and preparation method thereof |
| CN109022775A (en) * | 2018-06-27 | 2018-12-18 | 昆明理工大学 | A kind of high-speed rail Gold Concentrate under Normal Pressure acid thiourea extract technology |
| CN108998666A (en) * | 2018-07-27 | 2018-12-14 | 中南大学 | A method of soaking gold from arsenic-containing gold ore |
| WO2022245731A1 (en) * | 2021-05-17 | 2022-11-24 | Jetti Resources, Llc | Methods for liberating precious metals using a reagent having a thiocarbonyl functional group |
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