CN108546828A - A method of soaking gold using nickel ion, calcium thiosulfate - Google Patents
A method of soaking gold using nickel ion, calcium thiosulfate Download PDFInfo
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- CN108546828A CN108546828A CN201810457562.7A CN201810457562A CN108546828A CN 108546828 A CN108546828 A CN 108546828A CN 201810457562 A CN201810457562 A CN 201810457562A CN 108546828 A CN108546828 A CN 108546828A
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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
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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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of methods for soaking gold using nickel ion, calcium thiosulfate, and the solution containing nickel ion and calcium thiosulfate, which is added, into gold sulphide ores leaches the gold in gold sulphide ores.This method eliminates Cu (NH3)4 2+To S2O3 2‑Oxygenolysis, so that thiosulfate consumption is greatly reduced；Eliminate Cu (S2O3)2 3‑/Cu(S2O3)3 5‑The interference that gold is inhaled to resin reduces its competitive Adsorption in resin surface to gold, is conducive to resin adsorption method recycling golden in leachate, and a simple segment process can be used in the desorption of gold loaded resin；The addition for avoiding ammonium hydroxide, eliminates NH3Threat to air and water body environment.The golden rate of this method leaching is suitable with traditional copper ion, ammonia, Leaching of Gold Using Thiosulfate method, but which solve the consumption of traditional Leaching of Gold Using Thiosulfate method thiosulfate is high, environment is unfriendly, in leachate gold recycling hardly possible problem.
Description
Technical field
The present invention relates to technical field of wet metallurgy, and in particular to a kind of side for soaking gold using nickel ion, calcium thiosulfate
Method.
Background technology
Currently, cyaniding because technology maturation, it is simple for process the advantages that for a long time gold extraction industry dominate.But its
There are three significant deficiencies：(1) cyanide severe toxicity, seriously threatens ecological environment and human health；(2) to the leaching of difficult-treating gold mine
Go out that effect is poor, and gold mine more than China's one third is refractory ore；(3) the golden rate of leaching is slow, and extraction time is generally up to
24h.Therefore, the development significance of non-cyanide gold-leaching technology is great.Wherein, thiosulfate technique have that leaching agent is nontoxic and price just
Preferably, the advantages that golden rate is fast, good to the difficult-treating gold mines such as cupric and carbon leaching effect is soaked, is widely regarded as most potential non-
Cyaniding.With in global range to the attention further of environmental protection, phase of the people to review on thiosulfate leaching gold commercial Application
It waits being increasingly urgent to.
Review on thiosulfate leaching gold research starts prevailing in last century late nineteen seventies, its work is found by long-term research
Industry is that gold recycling is difficult in thiosulfate consumption height and leachate using existing main obstacle.Leaching of Gold Using Thiosulfate
Shown in overall reaction such as formula (1)：
4Au+8S2O3 2-+O2+2H2O→4Au(S2O3)2 3-+4OH- (1)
The reaction carries out very slow under the conditions of existing for no catalyst, as introducing Cu2+、NH3Afterwards, golden rate is soaked
It significantly improves.Cuprammonium catalytic mechanism is：NH3In anode-catalyzed Au+With S2O3 2-Complexation reaction, Cu (NH3)4 2+In cathode catalysis O2
Reduction.But Cu (NH3)4 2+With stronger oxidisability, while it is easy again by metastable S2O3 2-Oxidation, is allowed to be converted into
SxO6 2-(x≥3)、SO3 2-、SO4 2-Deng this is to cause S2O3 2-The big main reason of consumption.In addition, the use of ammonia also can be to ring
Border generates threat.NH in air3Safe level be 14mg/L, be put into a kind of gas similar with HCN toxicity, in water body
NH3Oxidation product nitrate can lead to algal blooms and polluted underground water.
Another problem that traditional copper ion, ammonia, Leaching of Gold Using Thiosulfate method face is that gold recycling is difficult in leachate.
Due to Au (S2O3)2 3-Negative electrical charge height, ligand S2O3 2-Active force between activated carbon surface active site is weak, ion dimensioning
The very little reasons such as larger cause activated carbon to inhale gold difficult.When recycling gold using method of cementation, thiosulfate oxidation product S0It covers
It covers in lowpriced metal surface, prevents the generation of displacement reaction.In addition, copper ion, which is also displaced solution, enters precipitation, lead to thick gold
Product grade is low, and follow-up refining cost is high.Solvent extraction requires height to clarity of solution, cannot directly be recycled from ore pulp
Gold.In addition, extractant and organic phase inevitably will be remained partly in the solution, it is unfavorable for solution recycling.Therefore, living
Property charcoal absorption, the methods of displacement precipitation and solvent extraction gold cannot be effectively recycled from thiosulfate leaching liquid.Ion
It is excellent that exchanger resin absorption method has that can recycle the golden, desorption of resin and regeneration can synchronously complete at normal temperatures directly from ore pulp etc.
Point is widely regarded as recycling the most promising method of gold from the leachate.But Cu (I) is in leachate mainly with Cu
(S2O3)2 3-/Cu(S2O3)3 5-Form exist, due to the similitude of ligand species, electronic structure etc., inevitably
To Au (S2O3)2 3-Strong competition is generated in the absorption of resin surface, to be adsorbed together with gold.Lead to the desorption of gold loaded resin
Must be using two-stage process (first segment desorbs copper, second segment desorption gold) to detach copper and gold, the complexity of two-stage process makes resin
Absorption method recycles the of high cost of gold.
Currently, the research in thiosulfate gold extracting field is focused primarily on the control of reaction condition, the use of additive, sulphur
The self-generating of thiosulfate, the substitution of cuprammonium catalyst system and catalyzing these aspect.The copper in the control aspect of reaction condition, leachate
The concentration of ion and dissolved oxygen is dynamic value, and it is extremely difficult in suitable range to control them in actual production.It is adding
The use aspect of agent, for certain types of gold mine, the use of certain additives has centainly the consumption for reducing thiosulfate
Effect, but there are matchings between additive and ore type.Do not occur being also generally substantially reduced thiosulfate at present
The additive of consumption.Have studies have shown that sulfide in pyrite during oxygen pressure alkali leaching can spontaneous nuclear transformation be thio sulphur
Hydrochlorate, and gold of the preservation in mineral is by the S of self-generating2O3 2-Leaching simultaneously.But the leaching gold system side reaction is more, to obtain
Satisfied leaching gold rate is relatively difficult.Ironweed acid and iron EDTA substitution cuprammoniums are catalyzed Leaching of Gold Using Thiosulfate, can significantly reduce S2O3 2-
Consumption, but it is very severe tight to the control of solution ph requirement, and leaching gold is imitated when containing the mineral such as pyrite, magnetic iron ore in ore
Fruit is undesirable.Also some researches show that copper ion, calcium thiosulfate gold leaching-out process can also replace traditional cuprammonium to be catalyzed thiosulfuric acid
Salt method, the existence form of Cu (II) is [(S in leachate2O3)3Cu.O2]5-, the complex ion oxidability is also relatively strong, will oxygen
Change S2O3 2-Cause leaching agent consumption high.And Cu (I) is still mainly Cu (S2O3)2 3-/Cu(S2O3)3 5-Form, severe jamming gold
Resin adsorption.
Invention content
The main purpose of the present invention is to provide a kind of methods for soaking gold using nickel ion, calcium thiosulfate, to solve to pass
Thiosulfate consumes high, unfriendly to environment, gold recycling hardly possible in leachate problem in the Leaching of Gold Using Thiosulfate method of system.
To achieve the goals above, the present invention provides a kind of method for soaking gold using nickel ion, calcium thiosulfate, Xiang Han
The solution containing nickel ion and calcium thiosulfate is added in gold mineral to leach the gold in gold sulphide ores.
Further, after the solution containing nickel ion and calcium thiosulfate being added into gold sulphide ores, nickel ion in ore pulp
Initial concentration is 0.01mol/L~0.05mol/L.
Further, after the solution containing nickel ion and calcium thiosulfate being added into gold sulphide ores, thiosulfuric acid in ore pulp
The initial concentration of calcium is 0.1mol/L~1.0mol/L.
Further, into gold sulphide ores be added the solution containing nickel ion and calcium thiosulfate after, adjust pH values of pulp to
Then 7.0-9.0 carries out the leaching of gold.
Further, it is added before the solution containing nickel ion and calcium thiosulfate into gold sulphide ores, first by gold sulphide ores
Broken, fine grinding then adjusts ore pulp mass concentration to 20%~40%.
Further, the leaching the specific steps are：It is 0 DEG C~55 DEG C, air atmosphere condition in ore pulp solution temperature
Under, leaching 6.0h~12.0h.
It applies the technical scheme of the present invention, traditional thiosulfate is replaced using nickel ion solution, thiosulfuric acid calcium solution
Copper sulphate, ammonium hydroxide and thiosulfate (sodium salt or ammonium salt) in gold leaching-out process.This method eliminates Cu (NH3)4 2+To S2O3 2-Oxygen
Change decomposition so that thiosulfate consumption is greatly reduced；Eliminate Cu (S2O3)2 3-/Cu(S2O3)3 5-Gold is inhaled to resin
Interference, hence it is evident that reduce S2O3 2-Decomposition product SxO6 2-The concentration of (x >=3), to reduce it in resin surface to the competing of gold
Absorption is striven, is conducive to resin adsorption method recycling golden in leachate, and since the complex ion of nickel is to Au (S2O3)2 3-Absorption nothing
Apparent competition, therefore a simple segment process can be used in the desorption of gold loaded resin；The addition for avoiding ammonium hydroxide, eliminates NH3To big
The threat of gas and water body environment.The golden rate of this method leaching is suitable with traditional copper ion, ammonia, Leaching of Gold Using Thiosulfate method, but it is solved
Having determined, traditional Leaching of Gold Using Thiosulfate method thiosulfate consumption is high, environment is unfriendly, the difficult problem of gold recycling in leachate.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As recorded in background technology, thiosulfate consumes in traditional copper ion, ammonia, Leaching of Gold Using Thiosulfate method
Height, ammonia environmental pollution are more serious, and recycling golden in leachate is more difficult, in order to solve this problem, this application provides
A method of soaking gold using nickel ion, calcium thiosulfate.
The present invention a kind of typical embodiment in, provide it is a kind of using nickel ion, calcium thiosulfate soak gold
Method includes the following steps：The solution containing nickel ion and calcium thiosulfate is added into gold sulphide ores by the gold in gold sulphide ores
It is leached.
The present invention passes through Ni using nickel ion solution and thiosulfuric acid calcium solution joint leaching gold2+-Ca2+-S2O3 2-With Ni3+-
Ca2+-S2O3 2-Compound complex ion forms oxidation-reduction pair, is catalyzed S2O3 2-With Au+Coordination, realize S2O3 2-Leaching gold.This method
Eliminate Cu (NH in traditional Leaching of Gold Using Thiosulfate method3)4 2+To S2O3 2-Oxygenolysis so that thiosulfate consume
Amount is greatly reduced；Eliminate Cu (S2O3)2 3-/Cu(S2O3)3 5-The interference of gold is inhaled to resin, hence it is evident that reduce S2O3 2-Decomposition product
SxO6 2-The concentration of (x >=3) is conducive to resin golden in leachate to reduce its competitive Adsorption in resin surface to gold
Absorption method recycles, and since the complex ion of nickel is to Au (S2O3)2 3-Absorption without apparent competition, therefore the desorption of gold loaded resin can adopt
With a simple segment process；The addition for avoiding ammonium hydroxide, eliminates NH3Threat to air and water body environment.This method leaching gold
Rate is suitable with traditional copper ion, ammonia, Leaching of Gold Using Thiosulfate method, but which solve traditional thio sulphur of Leaching of Gold Using Thiosulfate method
Hydrochlorate consumption is high, environment is unfriendly, the difficult problem of gold recycling in leachate.
In the leaching gold method of the present invention, if the initial concentration of nickel ion is too low, ideal catalytic action is not had, if nickel
The initial concentration of ion is excessively high, and the consumption of calcium thiosulfate can be caused high.The initial concentration of nickel ion is excellent in ore pulp of the present invention
Selected control system reduces thio sulphur as possible within the scope of 0.01mol/L~0.05mol/L while reaching ideal catalytic effect
The consumption of sour calcium.
In the leaching gold method of the present invention, if the initial concentration of calcium thiosulfate is too low, the leaching rate of gold can be made slow.This
The initial concentration of calcium thiosulfate is preferably controlled in 0.1mol/L~1.0mol/L in invention ore pulp.Within this range, you can reach
To the golden rate of suitable leaching, and the consumption of calcium thiosulfate is can control, is unlikely to lead to calcium thiosulfate exorbitant expenditure.
In the method for the invention, the pH of ore pulp system cannot it is too low can not be excessively high, if the pH of ore pulp is too low, thio sulphur
Hydrochlorate is unstable, if the excessively high nickel ions of pH will produce precipitation.In the present invention, it is added into gold sulphide ores containing nickel ion and thio
After the solution of calcium sulfate, pH values of pulp is preferably adjusted to 7.0-9.0, the leaching of gold is then carried out, can reduce thiosulfuric acid to the greatest extent
The consumption of calcium and nickel.
In the method for the invention, before nickel ion solution and thiosulfuric acid calcium solution is added, first gold sulphide ores are broken
It is broken and be finely ground to -74 μm of particles and account for 90% or more mass fraction, it adds water and adjusts ore pulp mass concentration to 20%~40%.It leaches
Specific steps include：To add the ore pulp after nickel ion solution and thiosulfuric acid calcium solution air atmosphere, 0 DEG C~55 DEG C
Leaching 6.0h~12.0h under temperature condition.With this condition, the golden rate of ideal leaching can be reached.
Below in conjunction with specific embodiment and reference examples, the invention will be further described, but should not be construed as to this
The limitation of invention protection domain.
The preparation of calcium thiosulfate：ATS (Ammonium thiosulphate) and calcium hydroxide in molar ratio 1:1 is added in reactor, in constant temperature
The NH in solution is excluded under the conditions of 45 DEG C3, obtain thiosulfuric acid calcium solution.
Material condition one：The obtained calcining of the oxidized roasting pretreatment of certain high-sulphur and high-arsenic gold concentrate, Au grades are
84.27g/t, Fe, S, As, Sb, Pb, Cu mass content is respectively 31.25%, 1.03%, 0.55%, 0.25%, 0.24%,
0.09%.Its mineral composition is mainly bloodstone and quartz.Table 1 is the golden chemical phase analysis result of the calcining.
Golden chemical phase analysis result in 1 calcining of table
Reference examples 1：
First by ore reduction, be finely ground to -45 μm and account for 90%, and it is 25% to adjust ore pulp to mass concentration.Then to this
It is respectively 0.03mol/L, 1.0mol/L, 0.5mol/L that copper sulphate, ammonium hydroxide, sodium thiosulfate to concentration are sequentially added in ore pulp.
Then slurry pH is adjusted to 10.0, finally under conditions of air atmosphere, 25 DEG C of temperature, rotating speed 200r/min with sodium hydroxide
Leaching 8.0h, golden leaching rate are 84.86%, and the consumption of sodium thiosulfate is 36.67kg/t raw materials.Your leach in liquid
Gold is adsorbed using basic resin Tulsion A-21S, and the desorption of gold loaded resin uses two-stage process (copper stripping liquid：
0.5mol/L(NH4)2S2O3；Golden stripping liquid：0.1mol/L Na2SO3+1.0mol/L NaCl).It is computed, it is golden in leachate
The resin adsorption method rate of recovery (adsorption rate × desorption efficiency) be 89.5%.
Embodiment 1：
Using the ore pulp with 1 same particle sizes of reference examples and mass concentration, nickel sulfate is first added to a concentration of 0.01mol/L,
Then calcium thiosulfate is added to a concentration of 0.3mol/L, slurry pH is adjusted to 8.0, in other leaching conditions with sodium hydroxide
Under the same conditions with reference examples 1, golden leaching rate is 84.97%, and the consumption of calcium thiosulfate is 17.41kg/t raw materials.Leaching
It is identical as reference examples 1 to go out recycling condition golden in liquid, but the desorption of gold loaded resin, using a segment process, the golden rate of recovery is
98.4%.
Embodiment 2：
Using the ore pulp with 1 same particle sizes of reference examples and mass concentration, nickel sulfate is first added to a concentration of 0.03mol/L,
Then calcium thiosulfate is added to a concentration of 0.5mol/L, slurry pH is adjusted to 8.0, in other leaching conditions with sodium hydroxide
Under the same conditions with reference examples 1, golden leaching rate is 85.26%, and the consumption of calcium thiosulfate is 18.16kg/t raw materials.Leaching
Go out that recycling condition golden in liquid is same as Example 1, the golden rate of recovery is 98.2%.
Embodiment 3：
Using the ore pulp with 1 same particle sizes of reference examples and mass concentration, nickel sulfate is first added to a concentration of 0.05mol/L,
Then calcium thiosulfate is added to a concentration of 1.0mol/L, slurry pH is adjusted to 9.0, in other leaching conditions with sodium hydroxide
Under the same conditions with reference examples 1, golden leaching rate is 86.46%, and the consumption of calcium thiosulfate is 18.87kg/t raw materials.Leaching
Go out that recycling condition golden in liquid is same as Example 1, the golden rate of recovery is 98.6%.
Material condition two：Certain gold floatation concentrate, the wherein grade of Au are 42.49g/t, the matter of Cu, Fe, Pb, S, As, Sb, C
It is respectively 0.20%, 16.93%, 0.19%, 14.25%, 5.40%, 0.67%, 0.80% to measure content.Its mineral composition is main
For pyrite and quartz.Table 2 is chemical phase analysis result golden in the gold floatation concentrate.
Golden chemical phase analysis result in 2 gold floatation concentrate of table
Reference examples 2：
First by ore reduction, be finely ground to -45 μm and account for 90%, and it is 20% to adjust ore pulp to mass concentration.Then at this
It is respectively 0.03mol/L, 1.0mol/L, 0.50mol/L that copper sulphate, ammonium hydroxide, sodium thiosulfate to concentration are sequentially added in ore pulp.
Then slurry pH is adjusted to 10.0, in air atmosphere, 25 DEG C of solution temperature, the condition that rotating speed is 200r/min with sodium hydroxide
Lower leaching 8.0h, golden leaching rate are 71.49%, and the consumption of sodium thiosulfate is 47.38kg/t raw materials.In leachate
The recycling condition of gold is identical as reference examples 1, and the golden resin adsorption method rate of recovery (adsorption rate × desorption efficiency) is 89.3%.
Embodiment 4：
Using the ore pulp with 2 same particle sizes of reference examples and mass concentration, nickel sulfate is first added to a concentration of 0.01mol/L,
Then calcium thiosulfate is added to a concentration of 0.3mol/L, slurry pH is adjusted to 8.0 with sodium hydroxide, other leaching conditions with
Reference examples 2 are identical, and golden leaching rate is 71.03%, and the consumption of calcium thiosulfate is 17.25kg/t raw materials.It is golden in leachate
Recycling condition it is same as Example 1, the golden rate of recovery is 98.3%.
Embodiment 5：
Using the ore pulp with 2 same particle sizes of reference examples and mass concentration, nickel sulfate is first added to a concentration of 0.03mol/L,
Then calcium thiosulfate is added to a concentration of 0.5mol/L, slurry pH is adjusted to 9.0 with sodium hydroxide, other leaching conditions with
Reference examples 2 are identical, and golden leaching rate is 72.32%, and the consumption of calcium thiosulfate is 17.61kg/t raw materials.It is golden in leachate
Recycling condition it is same as Example 1, the golden rate of recovery is 98.8%.
Embodiment 6：
Using the ore pulp with 2 same particle sizes of reference examples and mass concentration, nickel sulfate is first added to a concentration of 0.05mol/L,
Then calcium thiosulfate is added to a concentration of 1.0mol/L, slurry pH is adjusted to 9.0 with sodium hydroxide, other leaching conditions with
Reference examples 2 are identical, and golden leaching rate is 73.39%, and the consumption of calcium thiosulfate is 18.14kg/t raw materials.It is golden in leachate
Recycling condition it is same as Example 1, the golden rate of recovery is 98.6%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of method for soaking gold using nickel ion, calcium thiosulfate, which is characterized in that be added into gold sulphide ores and contain nickel ion
The gold in gold sulphide ores is leached with the solution of calcium thiosulfate.
2. according to the method described in claim 1, containing nickel ion and calcium thiosulfate it is characterized in that, being added into gold sulphide ores
Solution after, in ore pulp the initial concentration of nickel ion be 0.01mol/L~0.05mol/L.
3. according to the method described in claim 1, containing nickel ion and calcium thiosulfate it is characterized in that, being added into gold sulphide ores
Solution after, in ore pulp the initial concentration of calcium thiosulfate be 0.1mol/L~1.0mol/L.
4. according to the method described in claim 1, containing nickel ion and calcium thiosulfate it is characterized in that, being added into gold sulphide ores
Solution after, adjust pH values of pulp to 7.0-9.0, then carry out gold leaching.
5. according to the method described in claim 1, containing nickel ion and calcium thiosulfate it is characterized in that, being added into gold sulphide ores
Solution before, the first broken, fine grinding by gold sulphide ores then adjusts ore pulp mass concentration to 20%~40%.
6. according to the method described in claim 1, it is characterized in that, the leaching the specific steps are：In ore pulp solution temperature
Under the conditions of 0 DEG C~55 DEG C, air atmosphere, leaching 6.0h~12.0h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519025A (en) * | 2020-06-19 | 2020-08-11 | 青海铜业有限责任公司 | Method for leaching gold by using cobalt ions and calcium thiosulfate |
| CN114540635A (en) * | 2022-01-25 | 2022-05-27 | 中南大学 | Method for extracting gold by catalyzing thiosulfate |
-
2018
- 2018-05-14 CN CN201810457562.7A patent/CN108546828A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519025A (en) * | 2020-06-19 | 2020-08-11 | 青海铜业有限责任公司 | Method for leaching gold by using cobalt ions and calcium thiosulfate |
| CN114540635A (en) * | 2022-01-25 | 2022-05-27 | 中南大学 | Method for extracting gold by catalyzing thiosulfate |
| CN114540635B (en) * | 2022-01-25 | 2023-11-07 | 中南大学 | Method for extracting gold by catalyzing thiosulfate |
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Application publication date: 20180918 |
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