CN103866123A - Method for leaching valuable metals at high temperature by using acidophilus archaea - Google Patents
Method for leaching valuable metals at high temperature by using acidophilus archaea Download PDFInfo
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- CN103866123A CN103866123A CN201410136359.1A CN201410136359A CN103866123A CN 103866123 A CN103866123 A CN 103866123A CN 201410136359 A CN201410136359 A CN 201410136359A CN 103866123 A CN103866123 A CN 103866123A
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Abstract
The invention provides a method for leaching valuable metals at high temperature by using acidophilus archaea. The method comprises the steps of inoculating acidophilus archaea to a culture medium, carrying out stirred culture, so as to prepare a stock, continuing to culture, so as to obtain a stock culture, mixing with ore slurry and a culture medium until the temperature of the ore slurry rises to 40-100 DEG C and the concentration of strains in the ore slurry reaches 10<9> to 10<10>/ml, and carrying out conventional stirred leaching. According to the method, the characteristics of automatic temperature rise and mass propagation of acidophilus archaea are utilized, so that the temperature of the ore slurry automatically rises to 40-100 DEG C, the content of valuable metals in tailings is lowered below 0.1%, and the leaching rate reaches up to 85-99%; acidophilus archaea in refluxing slurry is sufficiently utilized and is continuously replenished to original ore slurry so as to participate in leaching, thus the leaching cost is reduced, and commercial applications, such as high leaching rate, low cost, wide adaptability and the like, are realized.
Description
Technical field
The present invention relates to a kind of metal wet method extracting method, especially a kind of use is had a liking for the method for sour archeobacteria high temperature leaching valuable metal, belongs to valuable metal wet method extractive technique field.
Background technology
The wet-leaching of the valuable metals such as copper, adopts dilute sulphuric acid to leach conventionally, or the sulfuric acid leaching of heating, and this acidleach method can not leach sulphided state and in conjunction with oxidation state thing phase.People have researched and developed Bioleaching technology for this reason, but only secondary sulphide ore are had to better effects, to primary sulfide ore because there being passivation to fail effectively to leach.With regard to regard to oxidation ratio, no matter acidleach or bacterium are soaked, and are all regarded as " cancer " in hydrometallurgy.The high temperature bacterium research of Abroad in Recent Years has clear improvement to the leaching of chalcopyrite, but also still can not reach business goal, forms industrialization technology.
Have a liking for picture eubacterium in sour archeobacteria structure, without the core of moulding, on molecular level more as eukaryote, as having histone and intron on DNA, insensitive to microbiotic, there is again its exclusive feature, as the cell walls without real simultaneously, only have the Etheric ester type cytolemma of one deck band protein, conventionally claim " protoplastis ".Having a liking for sour archeobacteria can utilize metallic sulfide can utilize again the electron energy in gangue mineral, concentrate and release energy at short notice, temperature is raise automatically, and sharply breeding simultaneously, thoroughly discharges by primary sulfide ore with in conjunction with the metal of oxidized ore fast by " oxidation " and " chylification " effect.But, also do not use the technology of having a liking for the valuable metals such as sour archeobacteria high temperature leaching copper at present.
Summary of the invention
In order to solve, leaching yield is low, cost is high, be difficult to the difficult problems such as commercial applications, the invention provides a kind of method of having a liking for sour archeobacteria high temperature leaching valuable metal.
The present invention is so a kind of technical scheme: a kind of method of having a liking for sour archeobacteria high temperature leaching valuable metal, is characterized in that through following each step:
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
5～10
6the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid water or production tail washings
Sodium sulphite 5～10g/L
Sulphur 5～10g/L
Ferrous sulfate 20～50g/L
Ammonium sulfate 1～3g/L
Dipotassium hydrogen phosphate 0.25～1g/L
Magnesium sulfate 0.25～1g/L
Copper sulfate 0.1～0.5g/L
pH 1.0～2.0
When lasting stir culture to mixture temperature reaches 35～40 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
5～10
6the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 3～5 days, until temperature stops while reaching 35～40 DEG C stirring, obtains mother's kind of cultivation;
(3) be below 3cm by being crushed to granularity containing the lump ore of valuable metal, then ore grinding to granularity is crossed 100 objects and is accounted for more than 90% or mistake 200 objects account for more than 69%;
(4) size mixing according to practical situation, then add sulfuric acid, to keep ore pulp acidity as 0.5 ~ 200g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
5～10
6the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 1～3g/L
Dipotassium hydrogen phosphate 0.25～1g/L
Magnesium sulfate 0.25～1g/L
Copper sulfate 0.1～0.5g/L
Continuously stirring, until temperature is increased to 40～100 DEG C, the bacterial classification concentration in ore pulp reaches 10
9～10
10individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=20～50:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 4～25 hours, collect the leaching slurry of last agitation vat; Simultaneously in leaching process, by the reciprocal the 2nd or/and the reciprocal the 3rd return to the 1st agitation vat or/and the 4th part that agitation vat overflows reciprocal leaches slurry, with in constantly adding raw pulp, supplement bacterial classification by the leaching slurry returning, the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional separation-extraction technology; Tail washings after separation and Extraction valuable metal or extraction tail washings return to step (4) for sizing mixing, or after routine neutralization, then through solid-liquid separation clear liquid and end slag, clear liquid returns to step (3) and/or step (4), end slag send stockyard.
In above-mentioned steps, wherein the step such as (1) (2) (5) only limits to the operation initial stage, belongs to disposable step, while entering conventional production, only needs (3) (4) (6) (7) step.
Sizing mixing of described step (4) is: when sulfur content of raw material≤0.5% quality than time, size mixing by the liquid-solid ratio of 0.9～1.25:1; When raw material sulfur-bearing is 0.5～40% mass ratio or raw material while being high-energy metal or metal alloy, size mixing by the liquid-solid ratio of 1.25～10:1; Ore pulp acidity is to adjust according to the actual demand of subsequent technique.
Preferably 65～96 DEG C of the temperature of the middle continuously stirring of described step (5).
The conventional separation-extraction technology of described step (7) is Extraction electrodeposition separation-extraction technology.
The residue of described step (7), after extraction tail washings or tail washings fully clean, is stacked after adding lime to be adjusted to neutrality again, washing lotion be incorporated in step (7) containing in the solution of valuable metal, participate in together conventional separation-extraction technology and obtain valuable metal.
It is described that to have a liking for sour archeobacteria be by commercial following species:
thermoplasma acidophilum(having a liking for acid heat protoplastis),
thermoplasma volcanium(hot volcanic protoplastis),
ferroplasm acidarmanus(having a liking for acid heat iron protoplastis),
sulfolobus solfataricus(soft sulfolobus solfataricus) and
sulfolobus-like(class sulfolobus solfataricus), mixes by same equal proportion, proves through application practice, and this is had a liking for sour archeobacteria and has following ecological biochemical character:
1, at 40～100 DEG C of temperature, all there is good leaching effect, 65～96 DEG C of optimum temperature ranges, the higher leaching velocity of temperature is faster, leaching yield is higher;
2, the sulfuric acid system that suitable acidity is 0.5～200g/L, best pH=1.0～2.0;
3, As
3+below 40g/L, Cu
2+below 80g/L, other metal ion is below 80g/L, and salinity all has no effect to this bacterial classification than the ore pulp weighing below 1.8, all can as usual leach;
4, height above sea level, outside air temperature just, does not all affect the leaching effect of this bacterial classification;
5, can, to have the low price sulphur of electron energy, at a low price iron or low price metal and simple organic matter in metalliferous mineral or gangue mineral as the energy, automatically slurry temperature be risen to 40～100 DEG C.
The present invention utilizes the above-mentioned ecological biochemical character of having a liking for sour archeobacteria to carry out the leaching of valuable metal just, specifically utilize automatic heating and amount reproduction feature, do not needing to drop under the prerequisite of heating installation, can make ore pulp automatic heating to 40～100 DEG C, in whipping process, valuable metal in leached tailings can drop to below 0.1% conventionally, and leaching yield is up to 85～99%; The part that only need once have high input in leaching process is containing bacterium ore pulp, just can be in continuous dosing, continuous leaching process, make full use of the sour archeobacteria of having a liking for refluxing in slurry and constantly add to participation leaching in raw pulp, save the regeneration culturing process of having a liking for sour archeobacteria, reduce and leach cost, realized the commercial applications such as high leaching yield, low cost, wide adaptability.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
5the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid tail washings
Sodium sulphite 8g/L
Sulphur 10g/L
Ferrous sulfate 20g/L
Ammonium sulfate 2g/L
Dipotassium hydrogen phosphate 1g/L
Magnesium sulfate 0.25g/L
Copper sulfate 0.1g/L
pH 2.0
When lasting stir culture to mixture temperature reaches 40 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
5the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 5 days, until temperature stops while reaching 38 DEG C stirring, obtains mother's kind of cultivation;
(3) contain valency metal lump ore (proportion 2.5, cupric 0.52%, iron content 2.90% by what take from Tibet Nimu copper mine, sulfur-bearing≤0.3%, account for 20～30% in conjunction with oxidation ratio, chalcopyrite accounts for 15～20%) to be crushed to granularity be below 3cm, then ore grinding to granularity is crossed 100 objects and accounted for more than 90%;
(4) size mixing by the liquid-solid ratio of 1:1, then add sulfuric acid, to keep ore pulp acidity as 2.5g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
6the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 2g/L
Dipotassium hydrogen phosphate 1g/L
Magnesium sulfate 0.5g/L
Copper sulfate 0.5g/L
Continuously stirring, until temperature is increased to 65 DEG C, the bacterial classification concentration in ore pulp reaches 10
9individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=30:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 16 hours, collect the leaching slurry of last agitation vat; Simultaneously in leaching process, leach slurry by the reciprocal the 2nd with the 3rd part that agitation vat overflows reciprocal and return to the 1st agitation vat, with in constantly adding raw pulp, supplement bacterial classification by the leaching slurry returning, the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional Extraction electrodeposition separation-extraction technology; Extraction tail washings after separation and Extraction valuable metal directly returns to step (4) for sizing mixing; Residue is after through extraction, tail washings fully cleans, stack again after adding lime to be adjusted to neutrality, washing lotion be incorporated in this step (7) containing in the solution of valuable metal, participate in together conventional separation-extraction technology and obtain valuable metal.Tailings copper grade is at 0.04 ~ 0.09%, and copper leaching rate reaches more than 85%.
In above-mentioned steps, (1) (2) (5) step only limits to the operation initial stage, belongs to disposable step, enters after conventional production, only needs (3) (4) (6) (7) step.
Embodiment 2
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
6the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid water
Sodium sulphite 5g/L
Sulphur 8g/L
Ferrous sulfate 40g/L
Ammonium sulfate 3g/L
Dipotassium hydrogen phosphate 0.25g/L
Magnesium sulfate 0.5g/L
Copper sulfate 0.5g/L
pH 1.5
When lasting stir culture to mixture temperature reaches 38 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
6the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 4 days, until temperature stops while reaching 35 DEG C stirring, obtains mother's kind of cultivation;
(3) from Jiangxi Guixi Smelter contain valency metal lump ore (containing S35%, As (III) 28%, Cu10%, copper is with chalcopyrite (CuFeS
2, CuFe
2s
3) be main, CuS
2, Cu
1.8s is auxiliary, and aggregate distributes, and rhenium is with ReS
2there is discrete distribution, rhenium-containing 800 ~ 1800g/t with Re form; The preoxidation of former technology utilization lime and sulfuric acid leaching, soak 500 ~ 700 grams of tons of slag rhenium-containing, and the average leaching yield of rhenium is 40 ~ 50%, and copper is not leached) because its natural 3cm of being less than saves fragmentation, cross 200 objects through ore grinding to granularity and account for more than 69%;
(4) size mixing by the liquid-solid ratio of 5:1, then add sulfuric acid, to keep ore pulp acidity as 200g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
5the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 1g/L
Dipotassium hydrogen phosphate 0.5g/L
Magnesium sulfate 0.25g/L
Copper sulfate 0.3g/L
Continuously stirring, until temperature is increased to 75 DEG C, the bacterial classification concentration in ore pulp reaches 10
10individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=20:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 25 hours, collect the leaching slurry of last agitation vat; In leaching process, the part that second-to-last agitation vat is overflowed leaches slurry and returns to the 1st agitation vat simultaneously, with in constantly adding raw pulp, supplements bacterial classification by the leaching slurry returning, and the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional Extraction electrodeposition separation-extraction technology; Extraction tail washings after separation and Extraction valuable metal directly returns to step (4) for sizing mixing; Residue is after through extraction, tail washings fully cleans, stack again after adding lime to be adjusted to neutrality, washing lotion be incorporated in this step (7) containing in the solution of valuable metal, participate in together conventional separation-extraction technology and obtain valuable metal.Agitation leach is soaked 80 grams of 0.15%, 25 hour leached mud rhenium-containings of slag cupric for 4 hours below ton; Copper rhenium leaching yield is respectively more than 99.8% and 90%.
(1) (2) (5) step in above-mentioned steps only limits to the operation initial stage, belongs to disposable step, enters after conventional production, only needs (3) (4) (6) (7) step.
Embodiment 3
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
6the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid is produced tail washings
Sodium sulphite 10g/L
Sulphur 5g/L
Ferrous sulfate 50g/L
Ammonium sulfate 1g/L
Dipotassium hydrogen phosphate 0.5g/L
Magnesium sulfate 1g/L
Copper sulfate 0.1g/L
pH 1.0
When lasting stir culture to mixture temperature reaches 35 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
5the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 3 days, until temperature stops while reaching 40 DEG C stirring, obtains mother's kind of cultivation;
(3) will from African copper ferrocobalt alloy lump ore (proportion 8.0, containing Cu40%, Co28%, S2.7%, Fe18%, thing coordinates and is divided into FeSi, Cu
5zn
8, Co
3c, Zn
3sb
2, (FeNi), Cu
5as
2, FeS, PbS; There is the characteristic of difficult mill and difficult corrosion, at present adopt that high-temperature fusion spraying solves ore grinding problems, High Temperature High Pressure oxidation technologies solve leaching problems more) to be crushed to granularity be below 3cm, then ore grinding to granularity is crossed 200 objects and accounted for more than 69%;
(4) size mixing by the liquid-solid ratio of 10:1, then add sulfuric acid, to keep ore pulp acidity as 50g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
6the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 3g/L
Dipotassium hydrogen phosphate 0.25g/L
Magnesium sulfate 1g/L
Copper sulfate 0.1g/L
Continuously stirring, until temperature is increased to 100 DEG C, the bacterial classification concentration in ore pulp reaches 10
10individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=50:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 18 hours, collect the leaching slurry of last agitation vat; Simultaneously in leaching process, leach slurry by the reciprocal the 2nd and the reciprocal the 3rd with the 4th part that agitation vat overflows reciprocal and return to the 1st agitation vat, with in constantly adding raw pulp, supplement bacterial classification by the leaching slurry returning, the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional Extraction electrodeposition separation-extraction technology; Extraction tail washings after separation and Extraction valuable metal directly returns to step (4) for sizing mixing; Residue is after through extraction, tail washings fully cleans, stack again after adding lime to be adjusted to neutrality, washing lotion be incorporated in this step (7) containing in the solution of valuable metal, participate in together conventional separation-extraction technology and obtain valuable metal.Tailings cupric and cobalt are all below 0.3%, and the leaching yield of copper and cobalt, respectively up to 99%, has more than 60% ferrous iron to be oxidized to ferric iron simultaneously, and solution ratio weighs 1.7.
In above-mentioned steps, wherein the step such as (1) (2) (5) only limits to the operation initial stage, belongs to disposable step, while entering conventional production, only needs (3) (4) (6) (7) step.
Embodiment 4
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
6the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid is produced tail washings
Sodium sulphite 10g/L
Sulphur 5g/L
Ferrous sulfate 20g/L
Ammonium sulfate 2g/L
Dipotassium hydrogen phosphate 1g/L
Magnesium sulfate 1g/L
Copper sulfate 0.3g/L
pH 1.5
When lasting stir culture to mixture temperature reaches 40 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
5the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 5 days, until temperature stops while reaching 35 DEG C stirring, obtains mother's kind of cultivation;
(3) the valency metal lump ore that contains from Wuding, Yunnan (is contained to Cu0.62%, Fe18%, S0.01%, thing coordinates and is divided into ruby copper, mineral are composed and are deposited granularity >=400 order and account for 87%, and raw material ratio weighs 2.5, and the copper leaching rate of the acidleach of heating is the highest only has 30%, the acidleach tailings copper 0.4～0.5% of heating) to be crushed to granularity be below 3cm, then ore grinding to granularity is crossed 100 objects and accounted for more than 90%;
(4) size mixing by the liquid-solid ratio of 0.9:1, then add sulfuric acid, to keep ore pulp acidity as 0.5g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
6the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 3g/L
Dipotassium hydrogen phosphate 0.5g/L
Magnesium sulfate 1g/L
Copper sulfate 0.3g/L
Continuously stirring, until temperature is increased to 40 DEG C, the bacterial classification concentration in ore pulp reaches 10
10individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=50:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 13 hours, collect the leaching slurry of last agitation vat; In leaching process, the 4th part that agitation vat overflows reciprocal leached to slurry and return to the 1st agitation vat simultaneously, with in constantly adding raw pulp, supplement bacterial classification by the leaching slurry returning, the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional Extraction electrodeposition separation-extraction technology; Extraction tail washings after separation and Extraction valuable metal directly returns to step (4) for sizing mixing; Residue is after through extraction, tail washings fully cleans, stack again after adding lime to be adjusted to neutrality, washing lotion be incorporated in this step (7) containing in the solution of valuable metal, participate in together conventional separation-extraction technology and obtain valuable metal.Tailings cupric is below 0.2%, copper leaching rate >=85%.
In above-mentioned steps, wherein the step such as (1) (2) (5) only limits to the operation initial stage, belongs to disposable step, while entering conventional production, only needs (3) (4) (6) (7) step.
Embodiment 5
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
6the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid is produced tail washings
Sodium sulphite 5g/L
Sulphur 5g/L
Ferrous sulfate 40g/L
Ammonium sulfate 2g/L
Dipotassium hydrogen phosphate 1g/L
Magnesium sulfate 0.3g/L
Copper sulfate 0.2g/L
pH 1.5
When lasting stir culture to mixture temperature reaches 40 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
5the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 5 days, until temperature stops while reaching 35 DEG C stirring, obtains mother's kind of cultivation;
(3) will contain valency metal lump ore (proportion 3.0 from card room, Yunnan copper mine, cupric 1.0%, iron content 18%, sulphur 0.023%, wherein in conjunction with oxidation ratio 45%, chalcopyrite ore accounts for 5%, free copper oxide 50%, heat acidleach copper leaching rate less than 50%, tailings copper grade 0.5～0.7%) to be crushed to granularity be below 3cm, then ore grinding to granularity is crossed 200 objects and accounted for more than 69%;
(4) size mixing by the liquid-solid ratio of 1.25:1, then add sulfuric acid, to keep ore pulp acidity as 5g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
6the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 3g/L
Dipotassium hydrogen phosphate 0.5g/L
Magnesium sulfate 0.2g/L
Copper sulfate 0.15g/L
Continuously stirring, until temperature is increased to 80 DEG C, the bacterial classification concentration in ore pulp reaches 10
10individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=30:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 20 hours, collect the leaching slurry of last agitation vat; In leaching process, the 4th part that agitation vat overflows reciprocal leached to slurry and return to the 1st agitation vat simultaneously, with in constantly adding raw pulp, supplement bacterial classification by the leaching slurry returning, the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional Extraction electrodeposition separation-extraction technology; Extraction tail washings after separation and Extraction valuable metal directly returns to step (4) for sizing mixing; Residue is after through extraction, tail washings fully cleans, stack again after adding lime to be adjusted to neutrality, washing lotion be incorporated in this step (7) containing in the solution of valuable metal, participate in together conventional separation-extraction technology and obtain valuable metal.Tailings cupric is below 0.2%, copper leaching rate >=85%.
In above-mentioned steps, wherein the step such as (1) (2) (5) only limits to the operation initial stage, belongs to disposable step, while entering conventional production, only needs (3) (4) (6) (7) step.
Claims (5)
1. have a liking for a method for sour archeobacteria high temperature leaching valuable metal, it is characterized in that through following each step:
(1) by having a liking for acid heat protoplastis, hot volcanic protoplastis, have a liking for the sour archeobacteria of having a liking for that acid heat iron protoplastis, soft sulfolobus solfataricus and class sulfolobus solfataricus be mixed to get by same equal proportion, by every mL substratum containing 10
5～10
6the amount of individual bacterial classification, is inoculated in following substratum:
Base fluid water or production tail washings
Sodium sulphite 5～10g/L
Sulphur 5～10g/L
Ferrous sulfate 20～50g/L
Ammonium sulfate 1～3g/L
Dipotassium hydrogen phosphate 0.25～1g/L
Magnesium sulfate 0.25～1g/L
Copper sulfate 0.1～0.5g/L
pH 1.0～2.0
When lasting stir culture to mixture temperature reaches 35～40 DEG C, obtain the original seed of cultivation;
(2) step (1) gained original seed is contained to 10 by every mL substratum again
5～10
6the amount of individual bacterial classification, is inoculated in the substratum identical with step (1), and stir culture 3～5 days, until temperature stops while reaching 35～40 DEG C stirring, obtains mother's kind of cultivation;
(3) be below 3cm by being crushed to granularity containing the lump ore of valuable metal, then ore grinding to granularity is crossed 100 objects and is accounted for more than 90% or mistake 200 objects account for more than 69%;
(4) ore pulp of step (3) is sized mixing, then add sulfuric acid, to keep ore pulp acidity as 0.5 ~ 200g/L;
(5) plant by every mL ore pulp containing 10 female step (2) gained
5～10
6the amount of individual bacterial classification, is inoculated in the ore pulp of step (4), then toward adding following substratum in this ore pulp:
Ammonium sulfate 1～3g/L
Dipotassium hydrogen phosphate 0.25～1g/L
Magnesium sulfate 0.25～1g/L
Copper sulfate 0.1～0.5g/L
Continuously stirring, until temperature is increased to 40～100 DEG C, the bacterial classification concentration in ore pulp reaches 10
9～10
10individual/mL, must contain bacterium ore pulp;
(6) raw pulp after step (4) is sized mixing is sent into agitation vat and is carried out conventional agitation leach, specifically: in the 1st agitation vat, constantly add raw pulp, and by the volume ratio containing bacterium ore pulp: raw pulp=20～50:100, add step (5) gained containing bacterium ore pulp, and keep the 1st the bacterial classification concentration in agitation vat to be not less than 10
8individual/mL, the 1st ore pulp that agitation vat automatic overflow goes out enters the 2nd agitation vat, and the 2nd ore pulp that agitation vat automatic overflow goes out enters the 3rd agitation vat, so continuously leaching valuable metal ore deposit step by step, until extraction time is 4～25 hours, collect the leaching slurry of last agitation vat; Simultaneously in leaching process, by the reciprocal the 2nd or/and the reciprocal the 3rd return to the 1st agitation vat or/and the 4th part that agitation vat overflows reciprocal leaches slurry, with in constantly adding raw pulp, supplement bacterial classification by the leaching slurry returning, the 1st the bacterial classification concentration in agitation vat is remained and be not less than 10
8individual/mL;
(7) the leaching slurry of step (6) being collected carries out after solid-liquid separation routinely, obtains solution and residue containing valuable metal, then solution is made to valuable metal through conventional separation-extraction technology; Tail washings after separation and Extraction valuable metal returns to step (4) for sizing mixing, or after routine neutralization, then through solid-liquid separation clear liquid and end slag, clear liquid returns to step (3) and/or step (4), end slag send stockyard.
2. the method for having a liking for sour archeobacteria high temperature leaching valuable metal according to claim 1, is characterized in that: sizing mixing of described step (4) is: when sulfur content of raw material≤0.5% quality than time, size mixing by the liquid-solid ratio of 0.9～1.25:1; When raw material sulfur-bearing is 0.5～40% mass ratio or raw material while being high-energy metal or metal alloy, size mixing by the liquid-solid ratio of 1.25～10:1; Ore pulp acidity is to adjust according to the actual demand of subsequent technique.
3. the method for having a liking for sour archeobacteria high temperature leaching valuable metal according to claim 1, is characterized in that: in described step (5), the temperature of continuously stirring is 65～96 DEG C.
4. the method for having a liking for sour archeobacteria high temperature leaching valuable metal according to claim 1, is characterized in that: the conventional separation-extraction technology of described step (7) is Extraction electrodeposition separation-extraction technology.
5. the method for having a liking for sour archeobacteria high temperature leaching valuable metal according to claim 1, it is characterized in that: after the residue tail washings of described step (7) fully cleans, after adding lime to be adjusted to neutrality, stack again, washing lotion is incorporated to containing in the solution of valuable metal in step (7), participates in together conventional separation-extraction technology and obtains valuable metal.
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