CN104131174A - Smelting method for comprehensive recovery of tin lead antimony silver zinc indium in bulk concentrate from ore dressing - Google Patents
Smelting method for comprehensive recovery of tin lead antimony silver zinc indium in bulk concentrate from ore dressing Download PDFInfo
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- CN104131174A CN104131174A CN201410367854.3A CN201410367854A CN104131174A CN 104131174 A CN104131174 A CN 104131174A CN 201410367854 A CN201410367854 A CN 201410367854A CN 104131174 A CN104131174 A CN 104131174A
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Abstract
The invention discloses a smelting method for comprehensive recovery of tin lead antimony silver zinc indium in bulk concentrate from ore dressing. The process comprises the following steps: (1) fuming enrichment: conducting fuming volatilizing on bulk concentrate, collecting fuming dust to obtain oxygen powder and sending the smelting slag to solid waste treatment; 2) haydrometallurgy of zinc: a, oxide powder recycle leaching; b. zinc after section recovery; and c, indium after section recovery; conducing separation treatment on zinc and crude indium to obtain acid leaching slag (lead mud); and (3) chlorine salt treatment: adding lead mud into a chlorine salt solution for leaching to obtain the leaching residue of antimony slag; conducting lead precipitation on the leaching solution to obtain lead slag, conducting zinc precipitation on the solution to obtain zinc and indium slag; returning zinc and indium slag to oxygen powder circulation in the step (2) for neutral leaching of feeding; and conducting concentration and evaporation on zinc deposition solution, and returning to the chlorine salt leaching for supplementing chlorine salt. The invention effectively utilizes the bulk concentrate obtained from dressing of the complex multi-metal oxide ore resource, and has advantages of comprehensive recycling of divalent metals, good environmental protection conditions, simple process and easiness to realize industrialized application, etc.
Description
Technical field
The present invention relates to non-ferrous metal metallurgy technical field, be specifically related to the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate.
Background technology
China's lead-zinc resource reserve is abundant, wherein low-grade refractory oxidized leadzinc ore resource has accounted for sizable ratio, for this part resource, owing to lacking efficient processing treatment technology, do not developed on a large scale yet at present, caused a large amount of wastes of resource.The Nandan County domestic large low-grade tin, lead and zinc multi-metal oxygen of factory's mining area surface ore reserves in Guangxi Hechi is abundant, only Barry--Longtoushan reaches more than 2,600 ten thousand tons once band reserves, in ore, contain the valuable metals such as tin, lead, antimony, silver, zinc, indium, wherein plumbous antimony is symbiosis, silver is composed and is existed in lead ore, and indium is composed and existed in zinc ore.In this ore, various metal contents are lower, and plumbous zinc oxidation ratio is all more than 90%, and this ore, because complicated difficult selects, not yet obtains effective development and utilization at present.With other from different places be that in this area's zinc oxide ore, leaded zinc grade is low, and association has a large amount of valuable metals, is referred to as complex multi-metal oxidized ore.
For a long time, processing treatment for low-grade lead-zinc is by the method for single ore dressing or smelting mostly, do not take into full account ore dressing and smelt full-range reasonable link and global optimization, cause selecting smelting to be isolated, consequently fail to realize the Efficient Development utilization of low-grade lead-zinc always.
Feature based on this earth's surface low-grade tin, lead and zinc multi-metal oxygen lead ore, and can carry out the comprehensive reality reclaiming by smelting technology in conjunction with lead and zinc bulk concentrate product, in the beneficiation flowsheet of this oxidized ore, can obtain stanniferous 0.4-1%, leaded 3-7%, containing antimony 3-5%, argentiferous 200-500g/t, containing zinc 5-10%, basis containing the collective concentrate of indium 0.02-0.1% on, the present invention is proposed.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate is provided after a kind of comprehensive recovery ore dressing, it has solved collective concentrate because each valuable constituent grade is low, is difficult to the problem of enriching and recovering.The present invention adopts pyrogenic process to combine with hydrometallurgy, realize the efficient recovery of the plumbous antimony silver of tin zinc indium, and the rate of recovery is higher.
To achieve these goals, the present invention has adopted following technical scheme:
A smelting process for the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing, comprises following processing step:
(1) fuming enrichment, by collective concentrate with the coal of 45-55% than mixing granulation, drop in fuming furnace or rotary kiln and carry out fuming volatilization, fuming volatilization temperature is 1400-1600 ℃, time 60-90min, metallurgical slag is sent to solid waste processing enter and reclaims wherein coal dust and other valuable metals; Volatilization flue dust obtains oxygen powder through the collecting method of conventional pyrogenic process.
(2) zinc hydrometallurgy, comprises following operation:
A) oxygen powder circulating leaching, the oxygen powder of step (1) fuming enrichment is carried out to neutrality to be leached, add the electrolytic zinc waste liquid of the sour 160-180g/l that begins to do end liquid, by liquid-solid ratio 3-4:1, drop into oxygen powder, temperature is controlled at 75-80 ℃, reaction 60-90min, then adjust terminal PH to 4.5-5.0 with oxygen powder, continue to stir 30～40min, filter.Neutral leaching residue enters indium back segment recovery process, leaches supernatant liquor and returns to neutral leaching barrel as leaching end liquid again, and so circulating leaching is 1-3 time.
B) zinc back segment reclaims, and by after a) operation circulating leaching, zinc concentration reaches the circulating leaching liquid of 80-100g/l after conventional deironing, purifying, and obtains the new liquid of electrodeposition, then obtains cloudy long-pending zinc through low zinc electrolytic process, then after conventional founding, obtains zinc ingot metal product;
As further illustrating of scheme, the new liquid of electrodeposition is containing zinc 80-100g/l.Adopt low zinc electrolytic process, control current density 300-400A/m
2, bath voltage 3-5V, in 36～48 hours zinc cycles of stripping, cloudy long-pending zinc, after conventional founding, obtains the zinc ingot metal product containing zinc 99.99%-99.995%.
C) indium back segment reclaims: by a) neutral leaching residue of operation output, by liquid-solid ratio, be that 2-3:1 drops in the reaction container of the vitriol oil mixture that is added with electrolysis waste solution (electrolytic zinc waste liquid) and massfraction 98%, temperature of reaction is controlled at 85-90 ℃, by the dense 90-120min that soaks of liquid-solid ratio 2:1, then mend clear water to the rare 40-60min of soaking of liquid-solid ratio 4～5:1.Reaction finish rear solution by routine purify, after indium extraction, removal of impurities, displacement, founding, acquisition contains the thick indium product of indium 98.5-99.5%; Slag is plumbous mud;
(3) villaumite is processed: comprise following operation:
D) villaumite leaches, and the plumbous mud of step (2) is dropped into the reaction container that is added with chloride solution by liquid-solid ratio 3-5:1, and temperature is controlled at 60-80 ℃, after reaction 90-120min, filters, and filter residue is antimony residue product; Filtrate send subsequent processing heavy plumbous;
E) heavy plumbous, toward d) add sulfate liquor in the filtrate of operation output, after reaction 30-60min, filter, filter residue is lead skim, and lead skim is lead skim product after washing; Filtrate is given next step heavy zinc; Described sulfate liquor concentration is 40-60g/l.
F) heavy zinc adds lime or alkali in the filtrate of e operation output, adjusts pH value to 5.5-6.5, after reaction 30-60min, filters, and filter residue send step (2) zinc hydrometallurgy; Filtrate is given next step concentration and evaporation;
G) concentration and evaporation, carries out the filtrate of f operation after concentration and evaporation, vaporize water can retrieval system as clear joint water of productive use, after evaporation, underflow returns to d) operation supplements villaumite.
Smelting process of the present invention for the stanniferous 0.4-1% of collective concentrate, leaded 3-7%, containing antimony 3-5%, argentiferous 200-500g/t, containing zinc 5-10%, containing indium 0.02-0.1%.
During step in the present invention (3) villaumite is processed, the villaumite of employing is sodium-chlor, Repone K or ammonium chloride etc.; Vitriol is sodium sulfate, potassium sulfate or ammonium sulfate etc., and sulfate liquor concentration is 40-60g/l.
In method of the present invention, plumbous mud composition is: stanniferous 2-3%, leaded 25-30%, containing antimony 15-20%, argentiferous 1000-2500g/t, containing zinc 2-5%, containing indium 0.005-0.1%.
Above-mentioned antimony residue product composition is: stanniferous 5-7%, containing antimony 40-50%, argentiferous 1000-2000g/t.
Above-mentioned lead skim product composition is: leaded 40-50%, argentiferous 3000-5000g/t.
Benefit effect of the present invention:
1, the invention solves collective concentrate after the ore dressing of complex multi-metal oxidized ore because each valuable constituent grade is low, be difficult to the problem of enriching and recovering.
2, the present invention combines with hydrometallurgy by pyrogenic process, has realized the efficient recovery to the plumbous antimony silver of tin in the collective concentrate after the ore dressing of complex multi-metal oxidized ore zinc indium, by the sale to product, can obtain certain economic benefit.
3, for the collective concentrate after the ore dressing of complex multi-metal oxidized ore, adopt technique scheme, technical process is simple, practical, can realize the efficient recovery of the plumbous antimony silver of tin zinc indium, and the rate of recovery is high, not only realized the comprehensive utilization of this kind of resource, the secondary resource after also making low-grade complex multi-metal oxygen ore deposit by ore dressing has obtained further processing, has avoided secondary resource waste and has alleviated the pollution to environment.
Accompanying drawing explanation
Fig. 1 is technical process of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment 1
A smelting process for the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing, with the collective concentrate composition that the low-grade tin, lead and zinc multi-metal oxygen green ore in mining area, geochronology obtains after ore dressing is: tin 0.54%, lead 5.74%, antimony 3.92%, silver-colored 493g/t, zinc 6.40%, indium 0.0226%.
Above-mentioned collective concentrate is pressed to following processing step:
(1) fuming enrichment: by collective concentrate and hard coal, the coal with 45%, than mixing granulation, drops in fuming furnace and carries out fuming volatilization, and temperature is 1400 ℃ of left and right, volatilization time 90min.The solid waste processing enter that is sent to metallurgical slag reclaims wherein coal dust and other valuable metals; Volatilization flue dust obtains oxygen powder through gathering dust, and send zinc hydrometallurgy operation.
(2) zinc hydrometallurgy: the oxygen powder of fuming enrichment is carried out to neutrality and leach, add the electrolytic zinc waste liquid of the sour 160-180g/l that begins to do end liquid, drop into oxygen powder by liquid-solid ratio 3:1, temperature is controlled at 75-80 ℃, reaction 60-70min, then adjust terminal PH to 4.5-4.7 with oxygen powder, continue to stir 30min, filter.After neutral leaching, supernatant liquor returns to the neutral bottoming of leaching again, so circulates 1 time.
The liquid (zinc concentration reaches 80-100g/l) after the leaching of 1 time that circulates, after conventional deironing, purifying, obtains the new liquid of electrodeposition.The new liquid of electrodeposition is containing zinc 80-100g/l.Adopt low zinc electrolytic process, control current density 400A/m
2, bath voltage 5V, in 48 hours zinc cycles of stripping, cloudy long-pending zinc, again through conventional founding, obtains zinc ingot metal (purity 99.99%-99.995%).
Neutral leaching residue leached mud drops into be added with in the reaction container that the vitriol oil of electrolysis waste solution and massfraction 98% mixes and carries out acidic leaching, control the sour 250g/l that begins, liquid-solid ratio 2:1, temperature of reaction is controlled at 85-90 ℃, the dense 90-100min that soaks, then mend clear water to liquid-solid ratio 4:1 leaching 40-50min.Reaction finishes rear solution and is purified, after indium extraction, removal of impurities, displacement, founding, obtained the thick indium product containing indium 98.5% by routine, and leached mud (plumbous mud) send villaumite processing further to reclaim wherein the valuable metals such as tin antimony lead is silver-colored.
(3) villaumite is processed: the reaction container that the plumbous mud of step (2) is added with to chloride solution (sodium-chlor) by liquid-solid ratio 3:1 input carries out villaumite leaching, temperature is controlled at 60-70 ℃, reaction times 90-100min, reaction finishes rear filtration, and filter residue is antimony residue product.
After leaching toward villaumite, in filtrate, add 50g/l sodium sulfate to sink plumbous, reaction times 45min, filters, and filter residue is lead skim, and lead skim is lead skim product after washing.
Toward adding in the filtrate after heavy lead sheet alkali sink zinc, adjust pH value to 5.5-6.0, reaction times 30-40min, filtration, filter residue returns to zinc hydrometallurgy operation and feeds intake.Heavy zinc concentrating filter liquor evaporation after, vaporize water is for other water of productive use or directly with peace and quiet water, arrange outward, after evaporation, the dense mass concentration of underflow villaumite reaches 50%, returns to villaumite and leaches and recycle.
All technical:
1, each component content of fuming enriched in oxygen powder and evaporation rate (%)
| Composition | Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Content | 18.45 | 1.41 | 10.54 | 17.44 | 0.06 | 1418 |
| Evaporation rate | 93 | 84.2 | 86.7 | 98 | 85.5 | 92.8％ |
2, front liquid (circulating leaching liquid) composition (g/l) of zinc back segment recycling in zinc hydrometallurgy
| Zn | Fe 2+ | Filtration velocity |
| 84 | 5.78 | 65.13kg/m2.h |
3, the front liquid composition (g/l) of indium back segment recycling in zinc hydrometallurgy
| Zn | H + | In | Fe 3+ | SiO 2 |
| 30.02 | 80 | 0.8 | 0.37 | 0.18 |
4, the plumbous mud composition (%) of zinc hydrometallurgy output
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 2.12 | 2.23 | 15.81 | 27.81 | 0.009 | 2232 |
5, antimony slag composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 0.1 | 6.3 | 44.95 | 2.05 | 0.0191 | 1010 |
6, lead skim composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Trace | 0.14％ | 0.13％ | 44.51％ | 0.0038％ | 3091 |
With this collective concentrate of this art breading, the plumbous antimony silver of tin zinc indium metal total yield: tin 80%, lead 92.31%, antimony 78.63%, silver 88.69%, zinc 84.24%, indium 80.64%.
Embodiment 2
A smelting process for the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing, with the collective concentrate composition that the low-grade tin, lead and zinc multi-metal oxygen green ore in mining area, geochronology obtains after ore dressing is: tin 0.96%, lead 6.82%, antimony 4.46%, silver-colored 354g/t, zinc 9.8%, indium 0.01%.
Above-mentioned collective concentrate is pressed to following processing step:
(1) fuming enrichment: by collective concentrate and hard coal, the coal with 55%, than mixing granulation, drops in fuming furnace and carries out fuming volatilization, and temperature is 1600 ℃ of left and right, volatilization time 60min left and right.The solid waste processing enter that is sent to metallurgical slag reclaims wherein coal dust and other valuable metals; Volatilization flue dust obtains oxygen powder through gathering dust, and send zinc hydrometallurgy operation.
(2) zinc hydrometallurgy: the oxygen powder of fuming enrichment is carried out to neutrality and leach, add the electrolytic zinc waste liquid of the sour 160-180g/l that begins to do end liquid, drop into oxygen powder by liquid-solid ratio 4:1, temperature is controlled at 75-80 ℃, reaction 80-90min, then adjust terminal PH to 4.8-5.0 with oxygen powder, continue to stir 40min, filter.After neutral leaching, supernatant liquor returns to the neutral bottoming of leaching again, so circulates 3 times.
The liquid (zinc concentration reaches 80-100g/l) after the leaching of 3 times that circulates, after conventional deironing, purifying, obtains the new liquid of electrodeposition.The new liquid of electrodeposition is containing zinc 80-100g/l.Adopt low zinc electrolytic process, control current density 400A/m
2, bath voltage 5V, in 48 hours zinc cycles of stripping, cloudy long-pending zinc, again through conventional founding, obtains zinc ingot metal (purity 99.99%-99.995%).
Neutral leaching residue leached mud drops into be added with in the reaction container that the vitriol oil of electrolysis waste solution and massfraction 98% mixes and carries out acidic leaching, control the sour 250g/l that begins, liquid-solid ratio 3:1, temperature of reaction is controlled at 85-90 ℃, the dense 100-120min that soaks, then mend clear water to liquid-solid ratio 5:1 leaching 50-60min.Reaction finishes rear solution and is purified, after indium extraction, removal of impurities, displacement, founding, obtained the thick indium product containing indium 99.5% by routine, and leached mud (plumbous mud) send villaumite processing further to reclaim wherein the valuable metals such as tin antimony lead is silver-colored.
(3) villaumite is processed: the reaction container that the plumbous mud of step (2) is added with to chloride solution (Repone K) by liquid-solid ratio 5:1 input carries out villaumite leaching, temperature is controlled at 70-80 ℃, reaction times 100-120min, reaction finishes rear filtration, and filter residue is antimony residue product.
After leaching toward villaumite, in filtrate, add 60g/l potassium sulfate to sink plumbous, reaction times 60min, filters, and filter residue is lead skim, and lead skim is lead skim product after washing.
Toward adding in the filtrate after heavy lead sheet alkali sink zinc, adjust pH value to 6.0-6.5, reaction times 50-60min, filtration, filter residue returns to zinc hydrometallurgy operation and feeds intake.Heavy zinc concentrating filter liquor evaporation after, vaporize water is for other water of productive use or directly with peace and quiet water, arrange outward, after evaporation, the dense mass concentration of underflow villaumite reaches 50% left and right, returns to villaumite and leaches and recycle.
All technical:
1, each component content of fuming enriched in oxygen powder and evaporation rate (%)
| Composition | Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Content | 20.63 | 1.87 | 11.36 | 19.22 | 0.07 | 1302 |
| Evaporation rate | 94 | 85.8 | 87.3 | 97 | 85.9 | 90.6％ |
2, the plumbous mud composition (%) of zinc hydrometallurgy output
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 5.02 | 2.97 | 19.87 | 30.10 | 0.012 | 1834 |
3, antimony slag composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 0.2 | 7.1 | 49.6 | 2.32 | 0.025 | 1980 |
4, lead skim composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Trace | 0.15％ | 0.14％ | 49.82％ | 0.004％ | 5010 |
With this collective concentrate of this art breading, the plumbous antimony silver of tin zinc indium metal total yield: tin 82%, lead 93.45%, antimony 80.21%, silver 90.12%, zinc 85.04%, indium 81.12%.
Embodiment 3
A smelting process for the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing, with the collective concentrate composition that the low-grade tin, lead and zinc multi-metal oxygen green ore in mining area, geochronology obtains after ore dressing is: tin 0.42%, lead 5.03%, antimony 3.14%, silver-colored 201g/t, zinc 5.2%, indium 0.035%.
Above-mentioned collective concentrate is pressed to following processing step:
(1) fuming enrichment: by collective concentrate and hard coal, the coal with 45%, than mixing granulation, drops in fuming furnace and carries out fuming volatilization, and temperature is 1500 ℃ of left and right, volatilization time 70min.The solid waste processing enter that is sent to metallurgical slag reclaims wherein coal dust and other valuable metals; Volatilization flue dust obtains oxygen powder through gathering dust, and send zinc hydrometallurgy operation.
(2) zinc hydrometallurgy: the oxygen powder of fuming enrichment is carried out to neutrality and leach, add the electrolytic zinc waste liquid of the sour 160-180g/l that begins to do end liquid, drop into oxygen powder by liquid-solid ratio 3:1, temperature is controlled at 75-80 ℃, reaction 60-70min, then adjust terminal PH to 4.5-4.6 with oxygen powder, continue to stir 30min, filter.After neutral leaching, supernatant liquor returns to the neutral bottoming of leaching again, so circulates 2 times.
The liquid (zinc concentration reaches 80-100g/l) after the leaching of 2 times that circulates, after conventional deironing, purifying, obtains the new liquid of electrodeposition.The new liquid of electrodeposition is containing zinc 80-100g/l.Adopt low zinc electrolytic process, control current density 300A/m
2, bath voltage 3V, in 36 hours zinc cycles of stripping, cloudy long-pending zinc, again through conventional founding, obtains zinc ingot metal (purity 99.99%-99.995%).
Neutral leaching residue leached mud drops into be added with in the reaction container that the vitriol oil of electrolysis waste solution and massfraction 98% mixes and carries out acidic leaching, control the sour 250g/l that begins, liquid-solid ratio 2:1, temperature of reaction is controlled at 85-90 ℃, the dense 90-110min that soaks, then mend clear water to liquid-solid ratio 4:1 leaching 40-50min.Reaction finishes rear solution and is purified, after indium extraction, removal of impurities, displacement, founding, obtained the thick indium product containing indium 99.0% by routine, and leached mud (plumbous mud) send villaumite processing further to reclaim wherein the valuable metals such as tin antimony lead is silver-colored.
(3) villaumite is processed: the reaction container that the plumbous mud of step (2) is added with to chloride solution (ammonium chloride) by liquid-solid ratio 3:1 input carries out villaumite leaching, temperature is controlled at 60-70 ℃, reaction times 90-100min, reaction finishes rear filtration, and filter residue is antimony residue product.
After leaching toward villaumite, in filtrate, add 55g/l ammonium sulfate to sink plumbous, reaction times 30min, filters, and filter residue is lead skim, and lead skim is lead skim product after washing.
Toward adding in the filtrate after heavy lead sheet alkali sink zinc, adjust pH value to 5.5-6.0, reaction times 40-50min, filtration, filter residue returns to zinc hydrometallurgy operation and feeds intake.Heavy zinc concentrating filter liquor evaporation after, vaporize water is for other water of productive use or directly with peace and quiet water, arrange outward, after evaporation, the dense mass concentration of underflow villaumite reaches 45%, returns to villaumite and leaches and recycle.
All technical:
1, each component content of fuming enriched in oxygen powder and evaporation rate (%)
| Composition | Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Content | 17.86 | 1.38 | 10.45 | 17.40 | 0.06 | 1523 |
| Evaporation rate | 92 | 83.8 | 86.4 | 97 | 85.3 | 93.0％ |
2, the plumbous mud composition (%) of zinc hydrometallurgy output
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 1.98 | 2..04 | 14.92 | 25.17 | 0.005 | 1050 |
3, antimony slag composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 0.05 | 5.01 | 40.12 | 1.85 | 0.018 | 1008 |
4, lead skim composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Trace | 0.12％ | 0.11％ | 40.21％ | 0.0025％ | 3012 |
With this collective concentrate of this art breading, the plumbous antimony silver of tin zinc indium metal total yield: tin 80%, lead 91.25%, antimony 78.35%, silver 88.34%, zinc 84.05%, indium 80.12%.
Embodiment 4
A smelting process for the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing, with the collective concentrate composition that the low-grade tin, lead and zinc multi-metal oxygen green ore in mining area, geochronology obtains after ore dressing is: tin 0.73%, lead 6.44%, antimony 4.25%, silver-colored 486g/t, zinc 8.1%, indium 0.066%.
Above-mentioned collective concentrate is pressed to following processing step:
(1) fuming enrichment: by collective concentrate and hard coal, the coal with 45%, than mixing granulation, drops in fuming furnace and carries out fuming volatilization, and temperature is 1450 ℃ of left and right, volatilization time 90min.The solid waste processing enter that is sent to metallurgical slag reclaims wherein coal dust and other valuable metals; Volatilization flue dust obtains oxygen powder through gathering dust, and send zinc hydrometallurgy operation.
(2) zinc hydrometallurgy: the oxygen powder of fuming enrichment is carried out to neutrality and leach, add the electrolytic zinc waste liquid of the sour 160-180g/l that begins to do end liquid, by liquid-solid ratio 3.5:1, drop into oxygen powder, temperature is controlled at 75-80 ℃, reaction 70-80min, with oxygen powder, adjust terminal PH to 4.5-4.8 again, continue to stir 40min, filter.After neutral leaching, supernatant liquor returns to the neutral bottoming of leaching again, so circulates 2 times.
The liquid (zinc concentration reaches 80-100g/l) after the leaching of 2 times that circulates, after conventional deironing, purifying, obtains the new liquid of electrodeposition.The new liquid of electrodeposition is containing zinc 80-100g/l.Adopt low zinc electrolytic process, control current density 350A/m
2, bath voltage 4V, in 42 hours zinc cycles of stripping, cloudy long-pending zinc, again through conventional founding, obtains zinc ingot metal (purity 99.99%-99.995%).
Neutral leaching residue leached mud drops into be added with in the reaction container that the vitriol oil of electrolysis waste solution and massfraction 98% mixes and carries out acidic leaching, control the sour 250g/l that begins, liquid-solid ratio 3:1, temperature of reaction is controlled at 85-90 ℃, the dense 100-120min that soaks, then mend clear water to liquid-solid ratio 5:1 leaching 60min.Reaction finishes rear solution and is purified, after indium extraction, removal of impurities, displacement, founding, obtained the thick indium product containing indium 99.3% by routine, and leached mud (plumbous mud) send villaumite processing further to reclaim wherein the valuable metals such as tin antimony lead is silver-colored.
(3) villaumite is processed: the reaction container that the plumbous mud of step (2) is added with to chloride solution (sodium-chlor) by liquid-solid ratio 4:1 input carries out villaumite leaching, temperature is controlled at 65-75 ℃, reaction times 100-110min, reaction finishes rear filtration, and filter residue is antimony residue product.
After leaching toward villaumite, in filtrate, add 60g/l sodium sulfate to sink plumbous, reaction times 50min, filters, and filter residue is lead skim, and lead skim is lead skim product after washing.
Toward adding in the filtrate after heavy lead sheet alkali sink zinc, adjust pH value to 6.0-6.5, reaction times 40-60min, filtration, filter residue returns to zinc hydrometallurgy operation and feeds intake.Heavy zinc concentrating filter liquor evaporation after, vaporize water is for other water of productive use or directly with peace and quiet water, arrange outward, after evaporation, the dense mass concentration of underflow villaumite reaches 50%, returns to villaumite and leaches and recycle.
All technical:
1, each component content of fuming enriched in oxygen powder and evaporation rate (%)
| Composition | Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Content | 18.78 | 1.69 | 11.08 | 17.98 | 0.08 | 1364 |
| Evaporation rate | 93 | 84.5 | 86.6 | 98 | 86.4 | 92.3％ |
2, the plumbous mud composition (%) of zinc hydrometallurgy output
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 3.74 | 2.59 | 18.24 | 26.48 | 0.015 | 2497 |
3, antimony slag composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| 0.1 | 5.9 | 46.35 | 2.05 | 0.018 | 1524 |
4, lead skim composition (%) in villaumite processing
| Zn | Sn | Sb | Pb | In | Ag(g/t) |
| Trace | 0.13％ | 0.15％ | 46.58％ | 0.0032％ | 4062 |
With this collective concentrate of this art breading, the plumbous antimony silver of tin zinc indium metal total yield: tin 81%, lead 93.20%, antimony 80.12%, silver 89.21%, zinc 85.47%, indium 81.84%.
Claims (10)
1. comprehensive reclaim after ore dressing a smelting process for the plumbous antimony silver of tin zinc indium in collective concentrate, it is characterized in that: comprise following processing step:
(1) fuming enrichment, by collective concentrate with the coal of 45-55% than mixing granulation, drop in fuming furnace or rotary kiln and carry out fuming volatilization, metallurgical slag is sent to solid waste processing enter; Volatilization flue dust obtains oxygen powder through gathering dust;
(2) zinc hydrometallurgy, comprises following operation:
A) oxygen powder circulating leaching, carries out neutrality by the oxygen powder of step (1) fuming enrichment and leaches, and adds electrolytic zinc waste liquid to do end liquid, by liquid-solid ratio 3-4:1, drops into oxygen powder, and 60-90min is leached in reaction, then adjusts terminal PH to 4.5-5.0 with oxygen powder, filters; Neutral leaching residue enters indium back segment recovery process, leaches supernatant liquor and returns to neutral leaching barrel as leaching end liquid again, and so circulating leaching is 1-3 time;
B) zinc back segment reclaims, and by a) operation is after circulating leaching, zinc concentration reaches the circulating leaching liquid of 80-100g/l after conventional deironing, purifying, and obtains the new liquid of electrodeposition, then obtains cloudy long-pending zinc through low zinc electrolytic process, then after conventional founding, obtains zinc ingot metal product;
C) indium back segment reclaims: by a) neutral leaching residue of operation output, by liquid-solid ratio, be that 2-3:1 drops into the dense 90-120min of soaking in the reaction container of the vitriol oil mixture that is added with electrolysis waste solution and massfraction 98%, controlling the sour acidity that begins is 200-250g/l; Add clear water to the rare 40-60min of soaking of liquid-solid ratio 4 ~ 5:1, reaction finishes rear solution and is purified, after indium extraction, removal of impurities, displacement, founding, obtained thick indium product by routine again; Slag is plumbous mud;
(3) villaumite is processed: comprise following operation:
D) villaumite leaches, and the plumbous mud of step (2) is dropped into the reaction container that is added with chloride solution by liquid-solid ratio 3-5:1, and temperature is controlled at 60-80 ℃, after reaction 90-120min, filters, and filter residue is antimony residue product; Filtrate send subsequent processing heavy plumbous;
E) heavy plumbous, toward d) add sulfate liquor in the filtrate of operation output, after reaction 30-60min, filter, filter residue is lead skim, and lead skim is lead skim product after washing; Filtrate is given next step heavy zinc;
F) heavy zinc, toward e) add lime or alkali in the filtrate of operation output, adjust pH value to 5.5-6.5, filter after reacting 30-60min, filter residue send step (2) zinc hydrometallurgy; Filtrate is given next step concentration and evaporation;
G) concentration and evaporation, by f) filtrate of operation carries out after concentration and evaporation, vaporize water can retrieval system as clear joint water of productive use, after evaporation, underflow returns to d) operation supplements villaumite.
2. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: the stanniferous 0.4-1% of described collective concentrate, leaded 3-7%, containing antimony 3-5%, argentiferous 200-500g/t, containing zinc 5-10%, containing indium 0.02-0.1%.
3. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: described step (1) fuming volatilization temperature is 1400-1600 ℃, and the time is 60-90min.
4. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, it is characterized in that: in described a) oxygen powder circulating leaching, electrowinning zinc waste liquid initial acidity is 160-180g/l, temperature of reaction is 75-80 ℃, reaction finishes, with oxygen powder, adjust after terminal PH to 4.5-5.0, continue to filter after stirring 30 ~ 40min.
5. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, it is characterized in that: described b) in zinc back segment removal process, the new liquid of electrodeposition contains zinc 80-100g/l, then adopts the electrolysis of low zinc electrolytic process, controls current density 300-400A/m
2, bath voltage 3-5V, in 36 ~ 48 hours zinc cycles of stripping, obtains cloudy long-pending zinc, then after conventional founding, obtains the zinc ingot metal product containing zinc 99.99%-99.995%.
6. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: described c) indium back segment reclaims neutral leaching residue, and reaction extraction temperature is controlled at 85-90 ℃.
7. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: during described step (3) villaumite is processed, villaumite is sodium-chlor, Repone K or ammonium chloride; Vitriol is sodium sulfate, potassium sulfate or ammonium sulfate, and sulfate liquor concentration is 40-60g/l.
8. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: described plumbous mud composition is: stanniferous 2-3%, leaded 25-30%, containing antimony 15-20%, argentiferous 1000-2500g/t, containing zinc 2-5%, containing indium 0.005-0.1%.
9. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: described antimony residue product composition is: stanniferous 5-7%, containing antimony 40-50%, argentiferous 1000-2000g/t.
10. the smelting process of the plumbous antimony silver of tin zinc indium in collective concentrate after comprehensive recovery ore dressing according to claim 1, is characterized in that: described lead skim product composition is: leaded 40-50%, argentiferous 3000-6000g/t.
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| CN107955886A (en) * | 2017-12-08 | 2018-04-24 | 欧艳 | A kind of method that indium is extracted from rich indium alkali oxidation scum |
| CN111876608A (en) * | 2020-08-11 | 2020-11-03 | 广东省科学院资源综合利用研究所 | Comprehensive soot recovery method based on chloride leaching |
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