CN100371478C - Wet preprocessing method for difficult-to-treat gold ore containing arsenic and antimony - Google Patents
Wet preprocessing method for difficult-to-treat gold ore containing arsenic and antimony Download PDFInfo
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- CN100371478C CN100371478C CNB2006100087814A CN200610008781A CN100371478C CN 100371478 C CN100371478 C CN 100371478C CN B2006100087814 A CNB2006100087814 A CN B2006100087814A CN 200610008781 A CN200610008781 A CN 200610008781A CN 100371478 C CN100371478 C CN 100371478C
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Abstract
The present invention discloses a method for pretreating arsenic and antimony containing gold ore which is difficult to treat in a wet method and extracting gold without using cyanogen. Because micro and fine particle impregnating type arsenic and antimony containing gold ore contains hazardous elements, such as arsenic, antimony, sulfur, organic carbon, etc., the micro and fine particle impregnating type arsenic and antimony containing gold ore which is difficult to treat is difficult to extract in the conventional gold extracting method; in addition, the gold in a micro and fine particle impregnating type form is impregnated in the whole ore body, and accordingly, the gold is difficult to extract. The present invention adopts two procedures: the pretreatment in the wet method and the gold extraction without using the cyanogen, wherein the arsenic and the antimony are converted into soluble matters to be dissolved in water; the arsenic and the antimony are removed and changed into a state without influencing gold leaching. The present invention changes the traditional technological method for extracting the gold with cyanide so that the gold in the micro and fine particle impregnating type arsenic and antimony containing gold ore which is difficult to treat can be easily extracted, and the extraction rate can reach 70 to 95%. The present invention has the advantages of simple and convenient technology, environment protection requirement conformation and high extraction rate. The production capacity of the present invention can be rapidly formed.
Description
One, technical field
What the present invention relates to is a kind of method of carrying gold from Gold Ore, and what specially refer to is to contain the wet pretreatment of arsenic, antimony refractory gold ore and do not have the cyanogen gold extracting method.
Two, background technology
As everyone knows, at present, the method for carrying gold from gold containing ore mainly is that the auriferous ore of fine grinding is dissolved gold by prussiate, gold is extracted again.This is a kind of gold extracting method of routine.This conventional gold extracting method is effective for oxidation gold mine and general sulfuration gold mine.Yet this method contains arsenic, antimony refractory gold ore for micro-grain impregnation, is difficult to gold is proposed.In fact, the many areas of China are all being contained profuse micro-grain impregnation and are being contained arsenic, antimony difficult-treating gold mine resource.Because at present this class gold ore resource is not had better extraction way, therefore, mostly be in and treat development status.Micro-grain impregnation contains arsenic, why the antimony difficult-treating gold mine is difficult to extract with conventional gold extracting method, mainly be because contain harmful elements such as arsenic, antimony, sulphur, organic carbon in these class mineral, and gold is the form dip-dye of micro-grain impregnation in whole ore body, a part of embedding cloth is in the sulfurous iron ore thing, another is partly contaminated in mineral such as carbonate, silicate, mica, therefore, be difficult to extract.At present, when such gold mine is extracted, mainly contain two kinds of methods, but the first supplies smeltery's smelting gold to this part gold ore of flotation in the ore or gravity treatment, and dip-dye gold in the mineral such as carbonate, silicate, mica in ore can only be abandoned in useless mine tailing and can't reclaim.It two is to contain arsenic, antimony difficult-treating gold mine than higher micro-grain impregnation and directly carry out carrying out after the pre-treatment of pyrogenic process roasting oxidation cyaniding again and extract containing gold grade.The desirable extraction yield of this method is expected to reach 40-70%, yet the deadly defect of this method is difficult to the big production of scale exactly, and the flue dust environmental pollution that produces in the roasting is very big, duration and degree of heating temperature is difficult to grasp as easy as rolling off a log appearance " half-cooked " or " overdoing " phenomenon in the roasting.During ore roasting " half-cooked ", can form the arsenic in the ore, the leaching that antimony continues to disturb gold tricyanide.It is too strong to be ore roasting oxidation atmosphere when " overdoing ", and white arsenic is oxidized to arsenic powder, and generates arsenate and be fixed in the calcining, and arsenate can cover the surface of gold and wrap up gold again, has hindered the dissolving of gold in the cyaniding process.Therefore, the pyrogenic process roasting gold extracting method all is difficult to apply so far.Next technology that is applied to hot-pressure oxidation pre-treatment and PREPROCESSING OF A REFRACTORY GOLD still has certain degree of difficulty in the popularization of China.In addition, the industrial production that is applied to scale contains the method for extracting gold arsenic, the antimony difficult-treating gold mine from micro-grain impregnation, does not appear in the newspapers.
On the other hand, because being soluble in the prussiate, gold make prussiate in gold extracting method, become a kind of solvent of the most conventional use, yet the look that the powerful toxicity of prussiate makes people hear becomes, the degree of its environmental pollution is very serious, thereby, seek that a kind of not have the cyanogen gold extracting method be highly significant.And the present report of not seeing no cyanogen gold extracting method equally.
Three, summary of the invention
Purpose of the present invention just provides and a kind ofly contains the wet pretreatment of arsenic, antimony refractory gold ore and do not have the cyanogen gold extracting method.Contain the existing deficiency of gold extracting method arsenic, the antimony refractory gold ore to overcome to have now from micro-grain impregnation.
Realization of the present invention is based on such principle: contain in arsenic, the antimony difficult-treating gold mine at micro-grain impregnation, the principal element that hinders gold to propose is exactly arsenic and antimony, contain in arsenic, the antimony refractory gold ore at micro-grain impregnation and to remove arsenic and antimony, then gold just is easier to propose.Be dissolved in the water and arsenic and antimony are become soluble substance, just can remove arsenic and antimony.We know, the polysulfide of arsenus acid, thioarsenous acid, antimonous acid, thioantimonious acid or arsenic, antimony all is water-soluble, and arsenic and antimony are present in the refractory gold ore with sulphided form, they and alkaline oxidiser or base catalysis oxygenant react, and can generate the polysulfide of arsenus acid soluble in water, thioarsenous acid, antimonous acid, thioantimonious acid or arsenic, antimony.Thus, arsenic, antimony can be removed from refractory gold ore.The chemical equation of this process is:
A
S2S
3+6OH
-＝＝＝A
SO
3 3-+A
SS
3 3-+3H
2O ......(1)
S
b2S
3+6OH
-＝＝＝S
bO
3 3-+S
bS
3 3-+3H
2O ......(2)
A
S2S
3+3S
2-＝＝＝2A
SS
2- ......(3)
A
S2S
5+3S
2-＝＝＝2A
SS
4 3- ......(4)
S
b2S
3+3S
2-＝＝＝2S
bS
3 3- ......(5)
S
b2S
5+3S
2-＝＝＝2S
bS
4 3- ......(6)
In addition, containing arsenic, antimony refractory gold ore can also be with the pre-treatment of acidic oxidation curiumization, make arsenic and acid reactive chlorine reaction generation arsenic acid in the ore generate the no longer proposition of overslaugh gold of Tricalcium arsenate with the reaction of calcic basic cpd again, and make ore in sand form fully be oxidized to the oxide mineral that is easy to leach gold.The chemical equation of this process is:
4F
eS
2+15O
2+8H
2O＝＝＝2F
e2O
3+8H
2SO
4 .....(1)
4F
eA
sS+11O
2+2H
2O＝＝＝4HA
sO
2+4F
eSO
4 ...(2)
4F
eSO
4+2H
2SO
4+O
2＝＝＝2F
e2(SO
4)
3+2H
2O?....(3)
2HA
sO
2+O
2+2H
2O＝＝＝2H
3A
sO
4 ....(4)
F
e(SO
4)
3+2H
3A
sO
4＝＝＝2F
eA
sO
4↓ ....(5)
2H
3A
sO
4+3C
a(OH)
2＝＝＝C
a3(A
sO
4)
2↓+6H
2O...(6)
H
2SO
4+C
a(OH)
2＝＝＝C
aSO
4↓+2H
2O
After above-mentioned reaction, throw outs such as the ferric arsenate that generates, Tricalcium arsenate, calcium sulfate are more stable compounds, has the characteristic that not overslaugh gold leaches, after passing through the pre-treatment of acid chlorization curium oxide simultaneously, gold in the mineral and the reaction of acid reactive chlorine generate gold trichloride, this is the best condition that gold leaches, and can carry out that routine leached gold or gold is soaked in chlorination or thiosulphate soaks gold and reclaims gold.The chemical equation of the leaching process of the thiosulphate of the chlorination process of gold and gold is:
Cl
2+H
2O＝＝HClO+HCl
2Au+3Cl
2＝＝2AuCl
3
2Au+3Cl+3HClO＝＝2AuCl
3+3H
2O
AuCl
3+HCl＝＝H[AuCl
4]＝＝H
++[AuCl
4]
-
4Au+8S
2O
2- 3+2H
2O+O
2＝＝4Au(S
2O
3)
2- 2+4OH
-
2AuCl
3+4Na
2S
2O
3＝＝2Au(S
2O
3)
2 2-+3Cl
2+8Na
+
According to above-mentioned principle, technical scheme of the present invention is: a kind of wet pretreatment that contains arsenic, antimony refractory gold ore, and step is as follows:
(1) get contain active chlorine concentrations be 1.5-10% acid chlorization oxide compound agent solution with contain arsenic, antimony difficult-treating gold mine sand mixes, make the active chlorine concentrations in the per kilogram ore in sand form reach the 0.5-5 gram, transfer below the pH value to 1, and curium with cramps processing can directly be carried out conventional gold extraction or not have cyanogen gold and extract more than three days under 40-80 ℃ of condition.
(2) or with alkaline oxidiser or base catalysis oxygenant and water be made into the solution that concentration is 0.5-5%, and be 1 with the solid-liquid weight ratio: the ratio of 1-3 grinds to form 25-100 purpose microfine ore pulp with containing arsenic, antimony refractory gold ore under 25-80 ℃ condition;
(3) ore pulp that grinds is carried out gravity treatment, the concentrate that obtains can carry out conventional gold and refine, and solid-liquid separation is carried out in the water washing that isolated ore pulp and ore in sand form mixture are doubly measured with 2-5 more again, and isolated ore in sand form is standby or carry out conventional gold extraction, and waste water discards;
(4) get above-mentioned (3) isolated ore in sand form repeating step (1) again, the ore in sand form that obtains can carry out routine or not have cyanogen gold and extract.
Described acid chlorization oxidation panel mixture refers to by what chlorinated lime, sulfuric acid, hydrochloric acid or chlorine, hydrochloric acid, hydrogen peroxide or perchloric acid, hydrochloric acid, hydrogen peroxide or hydrochloric acid, hydrogen peroxide mixed and contains the mixing solutions that reactive chlorine is 1.5-10%.
Described curiumization refers to the mineral that will mix with the acidic oxidation composition, under the effect of chemical energy and heat energy, and the process of natural reaction.
Described alkaline oxidiser refers to sodium hydroxide or sodium sulphite or yellow soda ash or their equivalent arbitrary combination, and it is 3 with the weight ratio of clorox or chlorine that described base catalysis oxygenant refers to alkaline oxidiser: 0.5-1.5 mixes the resulting compound in back;
The concentration of percentage composition of the present invention is w/w (M/M) percentage concentration.
No cyanogen gold extracting method after a kind of wet pretreatment that contains arsenic, antimony refractory gold ore, step is as follows:
(1) gets chlorine, hydrochloric acid, salt and water and be made into the chloridizing leach solution that initial cl concn is the 0.8-2 grams per liter, and with solvent and solute weight ratio 0.5-3: 1 ratio adds above-mentioned in pretreated mineral, under 25-80 ℃ of condition, leached 5-20 hour, after the solid-liquid separation, leach liquor is standby, isolated slag back to nature;
(2) pH value of adjusting above-mentioned leach liquor with alkali is 5-6, fully replaces or fully adsorbs gold in the leach liquor with gac with zinc, gets final product.
(3) or get the ammoniacal liquor of thiosulphate, the 0.4-1 mole of 0.2-1 mole, the sulphite and the 0.4-1 gram cupric ion of 0.04-0.1 mole is made into ammoniac thiosulfate solution, with the solvent and solute weight ratio is 0.5-3: 1 ratio, add above-mentioned through pretreated and transfer pH value to the mineral of 9-11 with alkali, under 40-50 ℃ of condition, leached 8-20 hour, after the solid-liquid separation, leach liquor is standby, isolated slag back to nature;
(4) fully adsorb gold in the above-mentioned leach liquor with gac, get final product.
Take the present invention of above-mentioned measure, adopted wet pretreatment and no cyanogen to put forward gold two big steps.In the wet pretreatment process, the heat power of utilizing mechanochemical effect to produce, make the reaction of having quickened in arsenic in the mineral, antimony, the frequent collision of sulphur when ore grinding with alkaline oxidiser leaching agent or base catalysis oxidation leaching agent, it is soluble in water and remove to generate compounds such as the polysulfide of arsenus acid, thioarsenous acid, antimonous acid, thioantimonious acid or arsenic antimony of solubility or arsenic acid, metaantimmonic acid, sulfuric acid.After having removed the interference of these harmful elements, gold has just proposed than being easier to.In wet pretreatment, also carried out acid curium processing, this step makes in further acidifying oxidation of arsenic, sulphur in the mineral and the alkalescence and calcification, the compound that makes it to generate Tricalcium arsenate, calcium sulfate and arsenic, sulphur modification are become do not hinder gold to propose makes easier being suggested of gold in the mineral.Carry in the golden step at no cyanogen, utilize gold and chlorine reaction to generate gold trichloride and be dissolvable in water acid chloride and the characteristic of ammoniac thiosulfate, with acid reactive chlorine or thiosulphate gold is extracted respectively, thereby changed traditional processing method of carrying gold with prussiate.Utilize wet pretreatment of the present invention and do not have the cyanogen gold extracting method, can the gold that micro-grain impregnation contains in arsenic, the antimony difficult-treating gold mine successfully be extracted, look the difference of grinding particle size and degree of treatment, extraction yield can reach 70-95%, and technology of the present invention is easy, compliance with environmental protection requirements, the extraction yield height, easy to operate, cost is low, less investment, instant effect, can form throughput fast.
Four, embodiment
Embodiment 1
1, in water, adds 3 parts of sodium hydroxide and mix, be made into concentration and be 5% solution, and under 50 ℃ of conditions, grind to form 100 purpose microfine ore pulps with the ratio that 1 weight part contains arsenic, antimony refractory gold ore with 3 parts by weight solution with 1 part of clorox;
2, solid-liquid separation is carried out in the ore pulp dilution washing gravity treatment that grinds again, isolated ore in sand form can carry out routine and carry gold;
3 or the mineral after solid-liquid separation in add by what chlorinated lime, sulfuric acid, mixed in hydrochloric acid formed and contain the acid chlorization combination oxygenant that active chlorine concentrations is 1.5-10%, mix, make the active chlorine concentrations in the per kilogram mineral reach the 0.5-5 gram, transferring PH is 1, moisture content is 15%, sealing curiumization 7 days;
4,, can carry out routine and carry gold or gold is proposed with no cyanogen gold extracting method through pretreated mineral.
Embodiment 2
1, to contain arsenic, the antimony refractory gold ore carries out conventional ore grinding and gravity treatment, the gold ore that gravity treatment goes out is carried out routine and is smelted, the arsenic-containing gold ore sand that solid-liquid separation goes out is standby;
2, in treating refractory As-containing gold ore sand, add by what chlorine, hydrochloric acid, hydrogen peroxide mixed and contain the acid chlorization combination oxygenant that active chlorine concentrations is 1.5-10%, mix, make that the active chlorine concentrations in the per kilogram mineral is the 0.5-5 gram, transferring PH is 1, moisture content is 15%, sealing curiumization 7 days;
3,, can carry out routine and carry gold or gold is proposed with no cyanogen gold extracting method through above-mentioned pretreated mineral.
Embodiment 3
1, gets chlorinated lime, sulfuric acid, hydrochloric acid and be made into that to contain active chlorine concentrations be that acid chlorization oxide compound agent solution and the ore in sand form of 1.5-10% mixes, make the active chlorine concentrations in the per kilogram ore in sand form reach the 0.5-5 gram, transfer below the pH value to 1, and curium with cramps processing 7 days under 40-80 ℃ of condition;
2, get again by chlorine, hydrochloric acid, salt and water and be made into the chloridizing leach solution that initial cl concn is 2 grams per liters, and with 3 weight part chloridizing leach solutions and 1 weight part through the pretreated mineral of above-mentioned steps 1 together, under 50 ℃ of conditions, leached 10 hours, after the solid-liquid separation, leach liquor is standby, isolated slag back to nature;
3, the pH value of adjusting above-mentioned leach liquor with alkali is 5-6;
4, above-mentioned leach liquor adding zinc is fully replaced, and can propose gold.
Embodiment 4
1, gets chlorinated lime, sulfuric acid, hydrochloric acid and be made into that to contain active chlorine concentrations be that acid chlorization oxide compound agent solution and the ore in sand form of 1.5-10% mixes, make the active chlorine concentrations in the per kilogram ore in sand form reach the 0.5-5 gram, transfer below the pH value to 1, and curium with cramps processing 7 days under 40-80 ℃ of condition;
2, get 1 mole thiosulphate, 1 mole ammoniacal liquor, 0.1 mole S-WAT and 0.4 the gram cupric ion be made into ammoniac thiosulfate solution, with the solvent and solute weight ratio is 0.5-3: 1 ratio, add above-mentioned through pretreated and transfer pH value to the mineral of 9-11 with alkali, under 40-50 ℃ of condition, leached 8-20 hour, after the solid-liquid separation, leach liquor is standby, isolated slag back to nature;
3, fully adsorb gold in the above-mentioned leach liquor with gac, can propose gold.
Claims (3)
1. wet pretreatment that contains arsenic, antimony refractory gold ore is characterized in that described pre-treatment step is as follows:
(1) get contain active chlorine concentrations be 1.5-10% acid chlorization oxide compound agent solution with contain arsenic, antimony difficult-treating gold mine sand mixes, make the active chlorine concentrations in the per kilogram ore in sand form reach the 0.5-5 gram, transfer below the pH value to 1, and curium with cramps processing is directly carried out conventional gold extraction again or is not had cyanogen gold and extract more than three days under 40-80 ℃ of condition;
(2) or with alkaline oxidiser or base catalysis oxygenant and water be made into the solution that concentration is 0.5-5%, and be 1 with the solid-liquid weight ratio: the ratio of 1-3 grinds to form 25-100 purpose microfine ore pulp with containing arsenic, antimony refractory gold ore under 25-80 ℃ condition;
(3) ore pulp that grinds is carried out gravity treatment, the concentrate that obtains can carry out conventional gold and refine, and solid-liquid separation is carried out in the water washing that isolated ore pulp and ore in sand form mixture are doubly measured with 2-5 more again, and isolated ore in sand form is standby or carry out conventional gold extraction, and waste water discards;
(4) get above-mentioned (3) isolated ore in sand form repeating step (1) again, the ore in sand form that obtains carries out routine again or does not have cyanogen gold and extract;
Described acid chlorization oxidation panel mixture refers to by what chlorinated lime, sulfuric acid, hydrochloric acid or chlorine, hydrochloric acid, hydrogen peroxide or perchloric acid, hydrochloric acid, hydrogen peroxide or hydrochloric acid, hydrogen peroxide mixed and contains the mixing solutions that reactive chlorine is 1.5-10%;
Described curiumization refers to the mineral that will mix with the acidic oxidation composition, under the effect of chemical energy and heat energy, and the process of natural reaction;
Described alkaline oxidiser refers to sodium hydroxide or sodium sulphite or yellow soda ash or their equivalent arbitrary combination, and it is 3 with the weight ratio of clorox or chlorine that described base catalysis oxygenant refers to alkaline oxidiser: 0.5-1.5 mixes the resulting mixture in back.
2. the no cyanogen gold extracting method after a kind of wet pretreatment that contains arsenic, antimony refractory gold ore according to claim 1 is characterized in that described no cyanogen gold extracting method step is:
(1) gets chlorine, hydrochloric acid, salt and water and be made into the chloridizing leach solution that initial cl concn is the 0.8-2 grams per liter, and with solvent and solute weight ratio 0.5-3: 1 ratio adds above-mentioned in pretreated mineral, under 25-80 ℃ of condition, leached 5-20 hour, after the solid-liquid separation, leach liquor is standby, isolated slag back to nature;
(2) pH value of adjusting above-mentioned leach liquor with alkali is 5-6, fully replaces or fully adsorbs gold in the leach liquor with gac with zinc.
3. the no cyanogen gold extracting method after a kind of wet pretreatment that contains arsenic, antimony refractory gold ore according to claim 2 is characterized in that described no cyanogen gold extracting method step is:
(1) get the ammoniacal liquor of thiosulphate, the 0.4-1 mole of 0.2-1 mole, the sulphite and the 0.4-1 gram cupric ion of 0.04-0.1 mole is made into ammoniac thiosulfate solution, with the solvent and solute weight ratio is 0.5-3: 1 ratio, add above-mentioned through pretreated and transfer pH value to the mineral of 9-11 with alkali, under 40-50 ℃ of condition, leached 8-20 hour, after the solid-liquid separation, leach liquor is standby, isolated slag back to nature;
(2) fully adsorb gold in the above-mentioned leach liquor with gac.
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| CNB2006100087814A CN100371478C (en) | 2006-02-11 | 2006-02-11 | Wet preprocessing method for difficult-to-treat gold ore containing arsenic and antimony |
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| CNB2006100087814A CN100371478C (en) | 2006-02-11 | 2006-02-11 | Wet preprocessing method for difficult-to-treat gold ore containing arsenic and antimony |
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| CN100371478C true CN100371478C (en) | 2008-02-27 |
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