CN106636634B - A kind of technique for being catalyzed Leaching of Gold Using Thiosulfate - Google Patents

A kind of technique for being catalyzed Leaching of Gold Using Thiosulfate Download PDF

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CN106636634B
CN106636634B CN201611257286.7A CN201611257286A CN106636634B CN 106636634 B CN106636634 B CN 106636634B CN 201611257286 A CN201611257286 A CN 201611257286A CN 106636634 B CN106636634 B CN 106636634B
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thiosulfate
leaching
gold
sulfosalicylic acid
ore pulp
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CN106636634A (en
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徐斌
杨永斌
李骞
姜涛
刘晓亮
李光辉
郭宇峰
范晓慧
黄柱成
张元波
许斌
陈许玲
彭志伟
甘敏
杨凌志
易凌云
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • 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
    • 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)
  • Metallurgy (AREA)
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  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
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Abstract

It is golden to be catalyzed leaching that traditional thiosulfate technique need to add copper sulphate and ammoniacal liquor, but S2O3 2‑Easily by Cu (II) oxidation Decomposition, cause thiosulfate consumption big, and NH3Use can also produce larger threat to air and water body environment.The invention discloses a kind of new technology for being catalyzed Leaching of Gold Using Thiosulfate.The addition of ferric sulfate and sulfosalicylic acid or sulfosalicylic acid sodium salt substituted vitriol copper and ammoniacal liquor is added in Leaching of Gold Using Thiosulfate ore pulp.The technique significantly reduces the consumption of thiosulfate, and also eliminates the use of ammoniacal liquor, avoids NH3Threat to environment.In addition, the Leaching of Gold Using Thiosulfate rate of technique catalysis is worked as with traditional cuprammonium catalytic phase.

Description

A kind of technique for being catalyzed Leaching of Gold Using Thiosulfate
Technical field
The present invention relates to technical field of wet metallurgy, specifically a kind of technique for being catalyzed Leaching of Gold Using Thiosulfate.
Background technology
Cyaniding dominates in gold extraction industry for a long time because of technical maturity, low cost and other advantages.But due to cyanogen Compound severe toxicity, the leaching gold method easily pollute environment and endanger the health of worker in production.In addition, also there is leaching gold speed in cyaniding Rate is slow, it is impossible to the shortcomings of effectively leaching difficult-treating gold mine.Therefore, non-cyanide gold-leaching has become the focus of research.Numerous In non-Process for the cyanation, thiosulfate technique have soak golden agent is nontoxic, reagent is cheap, the golden speed of leaching is fast, can efficiently leach cupric and The advantages such as the difficult-treating gold mines such as carbonaceous, therefore it is widely believed that most potential substitution cyaniding.But current review on thiosulfate leaching Gold also rarely has commercial Application, and its existing bottleneck problem is that the golden agent consumption of leaching is big.The net reaction of review on thiosulfate leaching gold is such as Shown in formula (1), if presence without catalyst under normal temperature and pressure, the reaction carries out very slow.When introducing Cu in system (II)、NH3Afterwards, soak golden speed and improve 18~20 times.But metastable S2O3 2-With stronger reproducibility, easily by Cu (II) oxygen Change and decompose, generate SxO6 2-、SO3 2-、S2-Deng.This composition for allowing for gold leachate becomes extremely complex, is extremely unfavorable for The recycling of leachate and the recovery of gold, and partially decomposed product will be also adsorbed on goldc grains surface, cause Gold leaching difficult.This Outside, the use of ammonia also can produce threat to environment.NH in air3Safe level be 14mg/L, be put into similar to HCN toxicity A kind of gas；NH in water body3It is listed in similar with chloride toxicity.
4Au+8S2O3 2-+O2+2H2O→4[Au(S2O3)2]3-+4OH- (1)
It is high to solve the bottleneck problem of Leaching of Gold Using Thiosulfate commercial Application-leaching agent consumption.Research both domestic and external is main Concentrate on Cu2+The control of concentration and the molten amount of oxygen etc., additive using and the substitution that is catalyzed of cuprammonium for the use of these.Due to leaching Cu in liquid2+Molten amount of concentration, oxygen etc. is dynamic value, and it in suitable scope is extremely difficult that them are controlled in practical operation. For certain types of gold mine, the use of some additives has certain effect to the consumption for reducing thiosulfate.But add Matching between agent and ore type be present, do not occur the additive that generally can effectively reduce thiosulfate consumption also at present. Using ironweed acid, iron EDTA, nickel ammonia substitution cuprammonium catalysis Leaching of Gold Using Thiosulfate, leaching agent consumption can obviously reduce.But adopt During with ironweed acid, iron EDTA catalysis, must control pH value of solution 4.2~6.4, it is unfavorable that thiosulfate is stablized, and must also add Reagent-the thiocarbamide being potentially carcinogenic soaks golden speed to improve.When being catalyzed using nickel ammonia, the use of ammonia will be larger to environment generation Threaten.
To solve the problems, such as that leaching agent consumption existing for current review on thiosulfate leaching gold is high and ammonia threatening environment, spy propose The present invention.
The content of the invention
It is low it is an object of the invention to provide a kind of leaching golden agent consumption and to the new work of the small Leaching of Gold Using Thiosulfate of environmental threat Skill.
One kind catalysis Leaching of Gold Using Thiosulfate technique, adds ferric sulfate and sulfosalisylic in Leaching of Gold Using Thiosulfate ore pulp The addition of acid or sulfosalicylic acid sodium salt substituted vitriol copper and ammoniacal liquor.
Described catalysis Leaching of Gold Using Thiosulfate technique, initial concentration of the ferric sulfate in ore pulp be 0.005~ 0.02mol/dm3；The initial concentration of sulfosalicylic acid or sulfosalicylic acid sodium salt in ore pulp is 0.01~0.06mol/dm3。
Described catalysis Leaching of Gold Using Thiosulfate technique, the mol ratio of ferric sulfate and sulfosalicylic acid or sulfosalicylic acid sodium salt Scope is 1:2~1:3.
Described catalysis Leaching of Gold Using Thiosulfate technique, initial concentration of the thiosulfate in ore pulp be 0.1~ 1.0mol/dm3。
Described catalysis Leaching of Gold Using Thiosulfate technique, will contain first golden raw material is broken, wet-milling to -200 mesh account for 90% with On, it is 25~40% to add water to adjust ore pulp to mass concentration；Then toward adding a certain amount of ferric sulfate, sulfosalicylic acid in ore pulp Or sulfosalicylic acid sodium salt, thiosulfate is added afterwards, and adjusts pH values of pulp to 8.0~10.0 with sodium hydroxide；Finally in sky Gas atmosphere, 0~45 DEG C, 6.0~24.0h of gold is soaked under conditions of 100~300r/min of stir speed (S.S.).
The present invention can produce following effect during Leaching of Gold Using Thiosulfate：
1st, the leaching agent consumption of cuprammonium catalysis Leaching of Gold Using Thiosulfate is generally up to 20kg/tRaw materialMore than, and after using the present invention Consumption can be down to 6.0kg/tRaw materialBelow.
2nd, be advantageous to leachate recycling and leachate in golden recovery.Due to S in leaching process2O3 2-Oxidation Decomposition amount substantially reduces, therefore catabolite such as S in leachatexO6 2-、SO3 2-、S2-Deng concentration also substantially reduce, so as to be advantageous to The recycling of leachate and the recovery of GOLD FROM PLATING SOLUTION.
3rd, environmental protection is advantageous to.Present invention, avoiding the use of ammoniacal liquor, NH is eliminated3Threat to air and water body, simultaneously The sulfosalicylic acid or sulfosalicylic acid sodium toxicity used is low, and it is widely used as medicine intermediate and biochemical reagents, and human body is good for Health and Environmental security threaten small.
Embodiment
The present invention is further illustrated with reference to embodiment, is not intended to limit the present invention.
Material condition one：Certain quartz vein gold ore stone, wherein Au grade are 5.6g/t, and Fe, S, Cu content are respectively 5.33%th, 0.03%, 0.03%, main gangue is quartz.
Reference examples 1：First ore reduction, wet ball-milling to -200 mesh are accounted for 90%, and adjust ore pulp to mass concentration and be 40%.The backward ore pulp in sequentially add copper sulphate, ammoniacal liquor, sodium thiosulfate to respectively 0.03mol/dm3、1.0mol/ dm3、0.30mol/dm3.Then with sodium hydroxide regulation pH values of pulp be 10.0,25 DEG C, air atmosphere, stir speed (S.S.) 200r/ 6.0h is leached under conditions of min, golden leaching rate is 88.5%, and the consumption of sodium thiosulfate is 34.13kg/tRaw material。
Embodiment 1：Into the ore pulp as described in reference examples 1, ferric sulfate is first added to 0.005mol/dm3, sulfosalicylic acid Sodium is to 0.01mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, sodium thiosulfate is then added to 0.3mol/dm3, it is used in combination Sodium hydroxide regulation pH values of pulp is 8.0, and 8.0h, golden leaching are leached under the same conditions in other leaching conditions and reference examples 1 Rate is 88.8%, and the consumption of sodium thiosulfate is 4.82kg/tRaw material。
Embodiment 2：Into the ore pulp as described in reference examples 1, ferric sulfate is first added to 0.01mol/dm3, sulfosalicylic acid Sodium is to 0.02mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, ATS (Ammonium thiosulphate) is then added to 0.25mol/dm3, it is used in combination Sodium hydroxide regulation pH values of pulp is 8.0, and 8.0h, golden leaching are leached under the same conditions in other leaching conditions and reference examples 1 Rate is 89.3%, and the consumption of ATS (Ammonium thiosulphate) is 5.08kg/tRaw material。
Embodiment 3：Into the ore pulp as described in reference examples 1, ferric sulfate is first added to 0.02mol/dm3, sulfosalicylic acid Sodium is to 0.04mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, sodium thiosulfate is then added to 0.30mol/dm3, it is used in combination Sodium hydroxide regulation pH values of pulp is 8.0, and 6.0h, golden leaching are leached under the same conditions in other leaching conditions and reference examples 1 Rate is 90.2%, and the consumption of sodium thiosulfate is 5.44kg/tRaw material。
Material condition two：The grade of certain gold floatation concentrate, wherein Au is 42.49g/t, and Fe, S, C, Cu content are respectively 16.93%th, 14.25%, 0.80% and 0.2%, its main mineral constituent is pyrite and quartz.
Reference examples 2：First ore reduction, wet ball-milling to -200 mesh are accounted for 100%, and adjust ore pulp to mass concentration and be 25%.The backward ore pulp in sequentially add copper sulphate, ammoniacal liquor, sodium thiosulfate to respectively 0.03mol/dm3、1.0mol/ dm3、0.8mol/dm3.Then with sodium hydroxide regulation pH values of pulp be 9.5,25 DEG C, air atmosphere, stir speed (S.S.) 300r/min Under conditions of leach 12.0h, golden leaching rate is 67.4%, and the consumption of sodium thiosulfate is 55.46kg/tRaw material。
Embodiment 4：Into the ore pulp as described in reference examples 2, ferric sulfate is first added to 0.005mol/dm3, sulfosalicylic acid Sodium is to 0.015mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, sodium thiosulfate is then added to 1.0mol/dm3, it is used in combination Sodium hydroxide regulation pH values of pulp is 10.0, in other leaching conditions and reference examples 2 under the same conditions with 400r/min stirring Speed leaches 24.0h, and golden leaching rate is 67.8%, and the consumption of sodium thiosulfate is 5.21kg/tRaw material。
Embodiment 5：Into the ore pulp as described in reference examples 2, ferric sulfate is first added to 0.01mol/dm3, sulfosalicylic acid Sodium is to 0.03mol/dm3, ATS (Ammonium thiosulphate) is then added to 0.8mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, it is used in combination Sodium hydroxide regulation pH values of pulp is 9.5, in other leaching conditions and reference examples 2 under the same conditions with 400r/min stirring speed Degree leaches 16.0h, and golden leaching rate is 68.2%, and the consumption of ATS (Ammonium thiosulphate) is 5.58kg/tRaw material。
Embodiment 6：Into the ore pulp as described in reference examples 2, ferric sulfate is first added to 0.02mol/dm3, sulfosalicylic acid Sodium is to 0.06mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, sodium thiosulfate is then added to 1.0mol/dm3, it is used in combination Sodium hydroxide regulation pH values of pulp is 9.5, in other leaching conditions and reference examples 2 under the same conditions with 400r/min stirring speed Degree leaches 12.0h, and golden leaching rate is 69.0%, and the consumption of sodium thiosulfate is 5.85kg/tRaw material。
Material condition three：Calcining obtained by the oxidized roasting of certain high-sulphur and high-arsenic gold concentrate, wherein Au grade are 84.27g/ T, S, As, Cu content are respectively 1.03%, 0.55% and 0.09%.Its main mineral constituent is bloodstone and quartz.
Reference examples 3：First ore reduction, wet ball-milling to -200 mesh are accounted for 95%, and adjust ore pulp to mass concentration and be 33%.The backward ore pulp in sequentially add copper sulphate, ammoniacal liquor, sodium thiosulfate to respectively 0.03mol/dm3、1.0mol/ dm3、0.50mol/dm3.Then with sodium hydroxide regulation pH values of pulp be 10.0,25 DEG C, air atmosphere, stir speed (S.S.) 200r/ 10.0h is leached under conditions of min, golden leaching rate is 85.2%, and the consumption of sodium thiosulfate is 36.73kg/tRaw material。
Embodiment 7：Into the ore pulp as described in reference examples 3, ferric sulfate is first added to 0.01mol/dm3, sulfosalicylic acid To 0.03mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, sodium thiosulfate is then added to 0.50mol/dm3, and use hydrogen Sodium oxide molybdena regulation pH values of pulp is 9.0, and 10.0h, golden leaching rate are leached under the same conditions in other leaching conditions and reference examples 3 For 85.4%, the consumption of sodium thiosulfate is 4.89kg/tRaw material。
Embodiment 8：Into the ore pulp as described in reference examples 3, ferric sulfate is first added to 0.015mol/dm3, sulfosalicylic acid To 0.03mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, ATS (Ammonium thiosulphate) is then added to 0.40mol/dm3, and use hydrogen Sodium oxide molybdena regulation pH values of pulp is 8.5, and 10.0h, golden leaching rate are leached under the same conditions in other leaching conditions and reference examples 3 For 86.6%, the consumption of ATS (Ammonium thiosulphate) is 5.19kg/tRaw material。
Embodiment 9：Into the ore pulp as described in reference examples 3, ferric sulfate is first added to 0.02mol/dm3, sulfosalicylic acid To 0.04mol/dm3Instead of the ammoniacal liquor and copper sulphate in reference examples, ATS (Ammonium thiosulphate) is then added to 0.50mol/dm3, and use hydrogen Sodium oxide molybdena regulation pH values of pulp is 8.5, and 8.0h, golden leaching rate are leached under the same conditions in other leaching conditions and reference examples 3 For 87.0%, the consumption of ATS (Ammonium thiosulphate) is 5.48kg/tRaw material。

Claims (4)

1. a kind of technique for being catalyzed Leaching of Gold Using Thiosulfate, it is characterised in that add sulfuric acid in Leaching of Gold Using Thiosulfate ore pulp The addition of iron and sulfosalicylic acid or sulfosalicylic acid sodium salt substituted vitriol copper and ammoniacal liquor；To specifically contain first golden raw material it is broken, Wet-milling to -200 mesh account for more than 90%, and it is 25~40% to add water to adjust ore pulp to mass concentration；Then it is certain toward addition in ore pulp Ferric sulfate, sulfosalicylic acid or the sulfosalicylic acid sodium salt of amount, thiosulfate is added afterwards, and adjust pH values of pulp with sodium hydroxide To 8.0~10.0；Finally under conditions of air atmosphere, 0~45 DEG C, 100~300r/min of stir speed (S.S.) soak gold 6.0~ 24.0h。
2. catalysis Leaching of Gold Using Thiosulfate technique according to claim 1, it is characterised in that ferric sulfate is first in ore pulp Beginning concentration is 0.005~0.02mol/dm3；The initial concentration of sulfosalicylic acid or sulfosalicylic acid sodium salt in ore pulp be 0.01~ 0.06mol/dm3。
3. catalysis Leaching of Gold Using Thiosulfate technique according to claim 1 or 2, it is characterised in that ferric sulfate and sulfo group water The molar ratio range of poplar acid or sulfosalicylic acid sodium salt is 1:2~1:3.
4. catalysis Leaching of Gold Using Thiosulfate technique according to claim 1, it is characterised in that thiosulfate is in ore pulp Initial concentration be 0.1~1.0mol/dm3。
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CN110205499B (en) * 2019-05-22 2020-08-07 东北大学 Composite sulfate catalyzed citric acid-thiosulfate gold leaching process

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CN103409623A (en) * 2013-07-26 2013-11-27 中南大学 Method for reducing consumption of thiosulfate in gold leaching system
CN104789792B (en) * 2015-05-07 2016-09-07 中南大学 A kind of technique of nickel citrate catalysis Leaching of Gold Using Thiosulfate
CN105603185B (en) * 2016-01-12 2017-11-03 中南大学 A kind of method that cobalt, ethylenediamine tetra-acetic acid are catalyzed Leaching of Gold Using Thiosulfate
CN105624420B (en) * 2016-01-12 2017-09-29 中南大学 A kind of method that cobalt, ammonia are catalyzed Leaching of Gold Using Thiosulfate

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