CN104032145B - The method of a kind of extraction and isolation Ag, Cu from flotation of silver concentrate - Google Patents
The method of a kind of extraction and isolation Ag, Cu from flotation of silver concentrate Download PDFInfo
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Abstract
The present invention relates to technical field of wet metallurgy, the method for especially a kind of extraction and isolation Ag, Cu from flotation of silver concentrate, adopt thiocarbamide, urea combined cycle to leach, crystallisation by cooling thiocarbamide Cu, this crystallization contains more than Cu15%, containing about Ag2%, containing Pb0.04%, containing about Zn1%, Al plate displacement silver is continuous, and regenerates thiocarbamide, then adds thiocarbamide, add after urging and proposing agent, return second time thiocarbamide and leach; After circulating leaching 3-4 time, thiocarbamide Cu produces saturated crystallization, dissolves with rare H2SO4, after replacing Ag wherein with Cu again, with Zn powder substitution Cu or evaporative crystallization CuSO4.5H2O, after crystallization, liquid adopts A1 displacement silver continuous, and with Cu replace silver-colored silk floss be incorporated in 500 DEG C calcine after leach with H2SO4 or HNO3; Be AgCl with HCl precipitation Ag wherein, then with ammoniacal liquor and hydrazine hydrate mixed solution reduce 99.95% Ag powder, then ingot casting Ag ingot.
Description
Technical field
The present invention relates to technical field of wet metallurgy, the method for especially a kind of extraction and isolation Ag, Cu from flotation of silver concentrate.
Background technology
Flotation of silver concentrate is generally by adopting butylamine black powder or the butyl xanthate leaching slag that leaching residual gets off from zinc leaching residue or other argentiferous leached muds, it contains Ag and is about more than 2000g/t, containing Cu about more than 2%, containing Zn about more than 20%, containing Pb about more than 8%, containing about more than S18%, as can be seen here, in flotation of silver concentrate also containing a large amount of Ag, Cu, Zn, Pb raw material; For this reason traditional extracting method has: pyrometallurgical smelting, roast reduction process or pyrometallurgical smelting combine with thiocarbamide lixiviate and extract; Wherein pyrometallurgical smelting adopts high temperature to add Cu or Pb and carry out fire reduction melting, then carry out electrolysis Cu or Pb, and from the method for anode sludge recover silver, this method facility investment is large, technical process is long, production cost is high; Roast reduction process first flotation of silver concentrate is placed in 800 DEG C of upper oxidizing roastings, then adopts acid or villaumite or Na2SO3 to leach, then with formaldehyde or hydrazine hydrate reduction Ag powder; The method, when oxidizing roasting, produces a large amount of SO2 flue gases, causes environmental pollution; The extracting method that pyrometallurgical smelting combines with thiocarbamide lixiviate is: flotation of silver concentrate is placed in thiourea solution, first uses zinc dust precipitation Ag, obtains Ag continuous, then uses zinc dust precipitation Cu; And by the calcining of Ag silk floss, then add collecting agent Pb and slag former Na
2cO
3or borax, iron filings carry out fire reduction and must contain Ag precious metals containing lead, carry out thick Ag that cupellation obtains 99% again electrolysis obtain 99.15 or 99.97% smart Ag, although this method decreases facility investment, shorten technical process, its energy consumption is comparatively large, and production cost is higher.
" difficult leaching independent silver deposit flotation of silver concentrate extracts silver and golden method " as the patent No. to be " in a kind of agglomeration for iron mine smoke dust silver extracting method " of CN201310186779.6 and the patent No. be CN95119869.6 is the extraction of the silver in flotation of silver concentrate, adopt thiocarbamide in conjunction with pyrometallurgical smelting, improve the organic efficiency of silver preparation concentrate, shortened process, reduce facility investment, reduce production cost.But it is all also comparatively undesirable.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides the method for a kind of extraction and isolation Ag, Cu from flotation of silver concentrate, there is silver products quality can be ensured, the purity of the product obtained is high, thiocarbamide loss is little, avoids environmental pollution, it also avoid argentiferous precious metals containing lead and adopts energy consumption during pyrometallurgical smelting large, silver loss is large, the feature that cost is high.
Be achieved particular by following technical scheme:
A method of extraction and isolation Ag, Cu from flotation of silver concentrate, comprises the following steps:
(1) leach liquor preparation:
Choose thiocarbamide with urging and propose agent and carry out preparation leach liquor, wherein contain thiocarbamide in leach liquor and being 40-60g/l, carrying agent 4-7g/l containing urging;
(2) lixiviate:
1. be 3-5 by flotation of silver concentrate and leach liquor according to liquid-solid ratio, temperature is 80-90 DEG C, a lixiviate 4-5h, and filters and obtain leaching slag a and immersion liquid a;
2. be 3-5 according to liquid-solid ratio again by leaching slag a, being placed in temperature is that the thiocarbamide of 80-90 DEG C is urged and carried agent leach liquor, secondary lixiviate 4-5h, filters and obtains leaching slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate to carry out mixing with a leach liquor and forms leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. immersion liquid a is cooled to temperature is≤25 DEG C of crystallization treatment, obtains liquid after crystallized product and crystallization, then silver in liquid after adopting AL to replace crystallization under the temperature environment of 50-60 DEG C, after displacement 9-11h, obtains silver-colored tender crystalline mother solution;
5. to thiocarbamide in crystalline mother solution with urge propose agent content traditionally characterization processes detect, and the content adding thiocarbamide is 40-60g/l, the content proposing agent is urged to be after 4-7g/l, obtain the crystalline mother solution after adjustment, and the crystalline mother solution after adjustment is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. being the sulphuric acid soln of 50-60g/l by crystallized product and concentration, is 3-5 according to liquid-solid ratio, when adjustment pH value is 1-2, dissolves at 50-60 DEG C, obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. be placed in after temperature is the calcining furnace calcination processing 2-5h of 500-600 DEG C by adopting Cu displacement to obtain the continuous silver silk floss obtained of replace with Al of silver, then adopt concentration to be the acid solution of 200g/l, be 3-5 according to liquid-solid ratio, lixiviate 2-4h, obtains immersion liquid c and soaks slag c;
9. soak slag c and return continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, addition quantity of HCl mol ratio is HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, AgCl precipitation adopt reductive agent from normal temperature according to rate of warming be 5 DEG C/min heat reach 60-65 DEG C to temperature time, obtain Ag powder, namely complete the extraction of Ag in flotation of silver concentrate;
10. Cu is replaced the displaced liquid reduction or dry in silver-colored step, the extraction of Cu in flotation of silver concentrate can be completed.
Described urge that to propose agent be one in urea, sodium lignosulfonate or two kinds of mixtures.
Described urge carry agent be urea and sodium lignosulfonate two kinds of mixtures time, the mol ratio of urea and sodium lignosulfonate is (2-4): (1-3).
Described urge carry agent be urea and sodium lignosulfonate two kinds of mixtures time, the mol ratio of urea and sodium lignosulfonate is 3:2.
Described displaced liquid reduction adopts the reduction of Zn powder.
Described reductive agent refers to ammoniacal liquor-hydrazine hydrate.
Described acid solution is the one in sulfuric acid or nitric acid.
The reduction of described AgCl precipitation first adopts the ammoniacal liquor of 10% to carry out normal temperature washing to AgCl precipitation, the ammoniacal liquor of 20% is adopted to size mixing under normal temperature environment again, and stir, heat-up rate is adopted to be that 5 DEG C/min is when being warming up to 60-65 DEG C again, constant temperature adds hydrazine hydrate, when Ag no longer produces precipitation in solution, stop adding of hydrazine hydrate.
Described silver silk floss calcining is that the silver cemented out by AL is continuous under the environment of 600 DEG C, and after calcination processing 2h, adopting concentration to be the salpeter solution of 200g/l, is 4 according to liquid-solid ratio, lixiviate 4h;
Described silver silk floss calcining is that the silver cemented out by Cu is continuous under the environment of 500 DEG C, and after calcination processing 5h, employing sulfuric acid concentration is 200g/l, is 5 according to liquid-solid ratio, lixiviate 2h.
One in what described Al displacement silver adopted is Al powder or Al plate;
One in what described Cu displacement silver adopted is Cu powder or Cu plate.
Compared with prior art, technique effect of the present invention is embodied in:
1. by thiocarbamide leaching, the urea of 10% is added in thiourea solution, and leaching crystalline mother solution is carried out circulating leaching, the thiocarbamide copper in flotation concentrate is made to obtain enrichment, improve the rate of recovery of silver in flotation of silver concentrate and copper, make the rate of recovery of silver reach more than 99%, the rate of recovery of copper reaches more than 83%, reduces the flotation of silver concentrate slag of argentiferous and copper to the pollution of environment.
2. the mechanism by utilizing A1 and thiocarbamide not to produce complexing action adopts A1 to replace Ag and obtains Ag silk floss and thiocarbamide reproduction quality is guaranteed; Overcome thiocarbamide Zn crystallization and block pipeline, decrease the loss of thiocarbamide, reduce production cost.
3. by by continuous for Ag under the environment of about 500 DEG C after calcining; Adopt acidleach, AgCl precipitation, the technique of ammoniacal liquor and hydrazine hydrate reduction metal A g powder, obtain metal A g powder containing 99.95% purity again 1000 ~ 1100 DEG C of foundings, make founding rate be more than 95%; Overcome and adopt pyrometallurgical smelting containing Ag precious metals containing lead, then carry out cupellation, during electrolytic refining metal Ag, the long flow path had, Ag loss is large, the shortcoming that cost is high; Also overcome flotation Ag and carry out oxidizing roasting, containing SO2 flue gas, the shortcoming of contaminate environment.
Embodiment
Below in conjunction with concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Embodiment 1
A method of extraction and isolation Ag, Cu from flotation of silver concentrate, comprises the following steps:
(1) leach liquor preparation:
Choose thiocarbamide with urging and propose agent and carry out preparation leach liquor, wherein contain thiocarbamide in leach liquor and being 40g/l, carrying agent 4g/l containing urging;
(2) lixiviate:
1. be 3 by flotation of silver concentrate and leach liquor according to liquid-solid ratio, temperature is 80 DEG C, a lixiviate 4h, and filters and obtain leaching slag a and immersion liquid a;
2. be 3 according to liquid-solid ratio again by leaching slag a, being placed in temperature is that the thiocarbamide of 80 DEG C is urged and carried agent leach liquor, secondary lixiviate 4h, filters and obtains leaching slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate to carry out mixing with a leach liquor and forms leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. immersion liquid a is cooled to temperature is 25 DEG C of crystallization treatment, obtains liquid after crystallized product and crystallization, then silver in liquid after adopting AL to replace crystallization under the temperature environment of 50 DEG C, after displacement 9h, obtains silver-colored tender crystalline mother solution;
5. to thiocarbamide in crystalline mother solution with urge propose agent content traditionally characterization processes detect, and the content adding thiocarbamide is 40g/l, the content proposing agent is urged to be after 4g/l, obtain the crystalline mother solution after adjustment, and the crystalline mother solution after adjustment is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. being the sulphuric acid soln of 50g/l by crystallized product and concentration, is 3 according to liquid-solid ratio, when adjustment pH value is 1, dissolves at 50 DEG C, obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. be placed in after temperature is the calcining furnace calcination processing 2h of 500 DEG C by adopting Cu displacement to obtain the continuous silver silk floss obtained of replace with Al of silver, then adopt concentration to be the acid solution of 200g/l, be 3 according to liquid-solid ratio, lixiviate 2h, obtains immersion liquid c and soaks slag c;
9. soak slag c and return continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, addition quantity of HCl mol ratio is HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, AgCl precipitation adopt reductive agent from normal temperature according to rate of warming be 5 DEG C/min heat reach 60 DEG C to temperature time, obtain Ag powder, namely complete the extraction of Ag in flotation of silver concentrate;
10. Cu is replaced the displaced liquid reduction or dry in silver-colored step, the extraction of Cu in flotation of silver concentrate can be completed.
Described urge that to propose agent be urea.
Described displaced liquid reduction adopts the reduction of Zn powder.
Described reductive agent refers to ammoniacal liquor-hydrazine hydrate.
Described acid solution is sulfuric acid.
The reduction of described AgCl precipitation first adopts the ammoniacal liquor of 10% to carry out normal temperature washing to AgCl precipitation, the ammoniacal liquor of 20% is adopted to size mixing under normal temperature environment again, and stir, heat-up rate is adopted to be that 5 DEG C/min is when being warming up to 60 DEG C again, constant temperature adds hydrazine hydrate, when Ag no longer produces precipitation in solution, stop adding of hydrazine hydrate.
What described Al displacement silver adopted is Al powder;
What described Cu displacement silver adopted is Cu powder.
Embodiment 2
A method of extraction and isolation Ag, Cu from flotation of silver concentrate, comprises the following steps:
(1) leach liquor preparation:
Choose thiocarbamide with urging and propose agent and carry out preparation leach liquor, wherein contain thiocarbamide in leach liquor and being 60g/l, carrying agent 7g/l containing urging;
(2) lixiviate:
1. be 5 by flotation of silver concentrate and leach liquor according to liquid-solid ratio, temperature is 90 DEG C, a lixiviate 5h, and filters and obtain leaching slag a and immersion liquid a;
2. be 5 according to liquid-solid ratio again by leaching slag a, being placed in temperature is that the thiocarbamide of 90 DEG C is urged and carried agent leach liquor, secondary lixiviate 5h, filters and obtains leaching slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate to carry out mixing with a leach liquor and forms leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. immersion liquid a is cooled to temperature is 20 DEG C of crystallization treatment, obtains liquid after crystallized product and crystallization, then silver in liquid after adopting AL to replace crystallization under the temperature environment of 60 DEG C, after displacement 11h, obtains silver-colored tender crystalline mother solution;
5. to thiocarbamide in crystalline mother solution with urge propose agent content traditionally characterization processes detect, and the content adding thiocarbamide is 60g/l, the content proposing agent is urged to be after 7g/l, obtain the crystalline mother solution after adjustment, and the crystalline mother solution after adjustment is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. being the sulphuric acid soln of 60g/l by crystallized product and concentration, is 5 according to liquid-solid ratio, when adjustment pH value is 2, dissolves at 60 DEG C, obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. be placed in after temperature is the calcining furnace calcination processing 5h of 600 DEG C by adopting Cu displacement to obtain the continuous silver silk floss obtained of replace with Al of silver, then adopt concentration to be the acid solution of 200g/l, be 5 according to liquid-solid ratio, lixiviate 4h, obtains immersion liquid c and soaks slag c;
9. soak slag c and return continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, addition quantity of HCl mol ratio is HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, AgCl precipitation adopt reductive agent from normal temperature according to rate of warming be 5 DEG C/min heat reach 65 DEG C to temperature time, obtain Ag powder, namely complete the extraction of Ag in flotation of silver concentrate;
10. Cu is replaced the displaced liquid reduction or dry in silver-colored step, the extraction of Cu in flotation of silver concentrate can be completed.
Described urge that to propose agent be sodium lignosulfonate.
Described displaced liquid reduction adopts the reduction of Zn powder.
Described reductive agent refers to ammoniacal liquor-hydrazine hydrate.
Described acid solution is nitric acid.
The reduction of described AgCl precipitation first adopts the ammoniacal liquor of 10% to carry out normal temperature washing to AgCl precipitation, the ammoniacal liquor of 20% is adopted to size mixing under normal temperature environment again, and stir, heat-up rate is adopted to be that 5 DEG C/min is when being warming up to 65 DEG C again, constant temperature adds hydrazine hydrate, when Ag no longer produces precipitation in solution, stop adding of hydrazine hydrate.
What described Al displacement silver adopted is Al plate;
What described Cu displacement silver adopted is Cu plate.
Embodiment 3
A method of extraction and isolation Ag, Cu from flotation of silver concentrate, comprises the following steps:
(1) leach liquor preparation:
Choose thiocarbamide with urging and propose agent and carry out preparation leach liquor, wherein contain thiocarbamide in leach liquor and being 50g/l, carrying agent 5.5g/l containing urging;
(2) lixiviate:
1. be 4 by flotation of silver concentrate and leach liquor according to liquid-solid ratio, temperature is 85 DEG C, a lixiviate 4.5h, and filters and obtain leaching slag a and immersion liquid a;
2. be 4 according to liquid-solid ratio again by leaching slag a, being placed in temperature is that the thiocarbamide of 85 DEG C is urged and carried agent leach liquor, secondary lixiviate 4.5h, filters and obtains leaching slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate to carry out mixing with a leach liquor and forms leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. immersion liquid a is cooled to temperature is 15 DEG C of crystallization treatment, obtains liquid after crystallized product and crystallization, then silver in liquid after adopting AL to replace crystallization under the temperature environment of 55 DEG C, after displacement 10h, obtains silver-colored tender crystalline mother solution;
5. to thiocarbamide in crystalline mother solution with urge propose agent content traditionally characterization processes detect, and the content adding thiocarbamide is 50g/l, the content proposing agent is urged to be after 5.5g/l, obtain the crystalline mother solution after adjustment, and the crystalline mother solution after adjustment is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. being the sulphuric acid soln of 55g/l by crystallized product and concentration, is 4 according to liquid-solid ratio, when adjustment pH value is 1.5, dissolves at 55 DEG C, obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. be placed in after temperature is the calcining furnace calcination processing 3.5h of 550 DEG C by adopting Cu displacement to obtain the continuous silver silk floss obtained of replace with Al of silver, then adopt concentration to be the acid solution of 200g/l, be 4 according to liquid-solid ratio, lixiviate 3h, obtains immersion liquid c and soaks slag c;
9. soak slag c and return continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, addition quantity of HCl mol ratio is HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, AgCl precipitation adopt reductive agent from normal temperature according to rate of warming be 5 DEG C/min heat reach 63 DEG C to temperature time, obtain Ag powder, namely complete the extraction of Ag in flotation of silver concentrate;
10. Cu is replaced the displaced liquid reduction or dry in silver-colored step, the extraction of Cu in flotation of silver concentrate can be completed.
Described urge that to propose agent be urea and sodium lignosulfonate two kinds of mixtures, the mol ratio of urea and sodium lignosulfonate is 2:1.
Described displaced liquid reduction adopts the reduction of Zn powder.
Described reductive agent refers to ammoniacal liquor-hydrazine hydrate.
Described acid solution is sulfuric acid.
The reduction of described AgCl precipitation first adopts the ammoniacal liquor of 10% to carry out normal temperature washing to AgCl precipitation, the ammoniacal liquor of 20% is adopted to size mixing under normal temperature environment again, and stir, heat-up rate is adopted to be that 5 DEG C/min is when being warming up to 63 DEG C again, constant temperature adds hydrazine hydrate, when Ag no longer produces precipitation in solution, stop adding of hydrazine hydrate.
What described Al displacement silver adopted is Al powder;
What described Cu displacement silver adopted is Cu powder.
Embodiment 4
A method of extraction and isolation Ag, Cu from flotation of silver concentrate, on the basis of embodiment 1, described urging carry agent be urea and sodium lignosulfonate two kinds of mixtures time, the mol ratio of urea and sodium lignosulfonate is 4:3.
Described silver silk floss calcining is that the silver cemented out by AL is continuous under the environment of 600 DEG C, and after calcination processing 2h, adopting concentration to be the salpeter solution of 200g/l, is 4 according to liquid-solid ratio, lixiviate 4h;
Described silver silk floss calcining is that the silver cemented out by Cu is continuous under the environment of 500 DEG C, and after calcination processing 5h, employing sulfuric acid concentration is 200g/l, is 5 according to liquid-solid ratio, lixiviate 2h.
Other steps are with embodiment 1.
Embodiment 5
A method of extraction and isolation Ag, Cu from flotation of silver concentrate, on the basis of embodiment 2, described urging carry agent be urea and sodium lignosulfonate two kinds of mixtures time, the mol ratio of urea and sodium lignosulfonate is 3:2.
Described silver silk floss calcining is that the silver cemented out by AL is continuous under the environment of 600 DEG C, and after calcination processing 2h, adopting concentration to be the salpeter solution of 200g/l, is 4 according to liquid-solid ratio, lixiviate 4h;
Described silver silk floss calcining is that the silver cemented out by Cu is continuous under the environment of 500 DEG C, and after calcination processing 5h, employing sulfuric acid concentration is 200g/l, is 5 according to liquid-solid ratio, lixiviate 2h.
Other steps are with embodiment 2.
The concrete grammar that embodiment 6 technological experiment chamber interior are carried out and step
A method of extraction and isolation Ag, Cu from flotation of silver concentrate,
(1) oxygenant adds impact experiment and test with repeatedly circulation extracting efficiency: get flotation of silver concentrate material 600, detect and contain Ag2580g/t, Zn23.62%, Pb8.12%, Cu1.51%, S18.1%; Adopt H
2sO
450g/L, thiocarbamide 60g/L, urea 7g/L, hydrogen peroxide 20ml, be 85 DEG C in temperature, be mixed with leach liquor; And flotation concentrate is placed in leach liquor, carry out twice circulating leaching, and detect: the leaching yield 84.83% of Ag; And in circulating leaching process, adopt the test of hydrogen peroxide blank, visible, whether adding of hydrogen peroxide, for the leaching yield of silver without impact, then leached mud and leach liquor are carried out three circulating leachings, the second time of each circulation leaches the thiocarbamide pressing 10g/L, and the urea of 3g/L is added; Record: each leaching yield of Ag is respectively 86.1%, 89.04%, 93.3%.Leached mud is containing Zn21.8%, Pb10.2%, Ag170g/t, SiO
27.8%, Cu0.51%, Fe2.3%;
(2) extract the Cu in flotation concentrate: get step 1) in the first time Leaching In Thiourea Solutions fluid 1000ml of circulating leaching carry out being cooled to 25 DEG C, liquid after output red colored crystalline 20.5g and crystallization, detection draws: respectively containing Cu15.01%, Ag1.98%, Pb0.04%, Zn1.2%; Containing Ag3.8%, Cu28.5% after this crystallization 500 DEG C of calcinations, use rare H
2sO
4, adjustment PH is at 1.5,80 DEG C, Gu dissolve by liquid /=3, detects: leach liquor is containing Ag12.7g/L, Cu95g/L; With Cu sheet displacement silver, filtration silver silk floss, obtains liquid and silver is continuous; Vaporised liquid again, obtains CuSO
4.5H
2o;
(3) Ag in flotation concentrate is extracted: with step 2) liquid carries out the displacement of Ag at 70 DEG C with aluminium sheet after shown crystallization, and replace 10 hours, obtain silver-colored tender displaced liquid; Detect: in solution, Ag drops to 8.5mg/L from 203mg/L, rate of displacement 97.21%, gained Ag silk floss is containing Ag54%; Displaced liquid returns after adding by 10g/L thiocarbamide and 3g/L urea carries out circulating leaching, and detection draws: the leaching yield of the 4th circulation A g is 93.34%;
(4) reduction of Ag: by step 3) Gu shown Ag is continuous press liquid /=4 with HNO3 600 DEG C of calcinings after 2 hours, 200g/L leaches, a leaching yield 97.91%, immersion liquid is containing Ag91g/L, and leached mud is containing Ag3.49%, Pb21.8%, Zn1.1%, Cu1.57%, illustrates that Pb, Zn, Cu are leached less when Ag has not been leached; In this leach liquor, add HCl precipitate A gCl by HCl/Ag=1.1, deposition rate 99.99%, AgCl first adds the ammonia scrubbing of 10%, the ammoniacal liquor adding 20% is again sized mixing and is stirred, heating, it is complete to precipitin reaction to add hydrazine hydrate to 60 DEG C, and the reduction ratio of Ag is 99%, Ag opaque amount more than 99.95%; Ammonia scrubbing liquid water and hydrazine reduction Ag wherein obtain Ag powder and obtain 99.95%Ag ingot 1000 DEG C of foundings, founding rate 95.93% containing Ag96.3%, Ag powder.
As can be seen here, Cu and Ag undertaken in flotation of silver concentrate by the experimental technique that the experiment in embodiment 6 is concrete is extracted, do not need to add oxygenant in process and first oxidizing reaction carried out to the material in flotation of silver concentrate slag as seen, and oxygenant whether add extraction yield for Ag without any impact; But, simple thiocarbamide carry out extraction process and thiocarbamide combine with urea the leach liquor that forms carry out the extracting efficiency of lixiviate extraction process and leaching yield all more excellent; And through repeatedly circulating leaching liquid or leaching slag extraction leaching, improve the extraction rate to the silver in flotation of silver concentrate, copper, improve extraction rate, reduce cost recovery, dip circulation uses, and reduces environmental pollution; Metallic object is calcined, and avoids consumption and the discharge of high energy consumption and high pollution thing, has the significant value of environmental protection and economic benefit.
It is important to point out at this; above embodiment is only limitted to be further elaborated the concrete operation method of technical scheme of the present invention and understand; the further restriction to technical scheme of the present invention can not be understood to; what those skilled in the art made on this basis does not have outstanding essential characteristics and the innovation and creation of marked improvement with technical scheme of the present invention, still belongs to protection category of the present invention.
Claims (10)
1. a method of extraction and isolation Ag, Cu from flotation of silver concentrate, is characterized in that, comprise the following steps:
(1) leach liquor preparation: choose thiocarbamide with urging and propose agent and carry out preparation leach liquor, wherein contain thiocarbamide in leach liquor and being 40-60g/l, carrying agent 4-7g/l containing urging;
(2) lixiviate:
1. be 3-5 by flotation of silver concentrate and leach liquor according to liquid-solid ratio, temperature is 80-90 DEG C, a lixiviate 4-5h, and filters and obtain leaching slag a and immersion liquid a;
2. be 3-5 according to liquid-solid ratio again by leaching slag a, being placed in temperature is that the thiocarbamide of 80-90 DEG C is urged and carried agent leach liquor, secondary lixiviate 4-5h, filters and obtains leaching slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate to carry out mixing with a leach liquor and forms leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. immersion liquid a is cooled to temperature is≤25 DEG C of crystallization treatment, obtains liquid after crystallized product and crystallization, then silver in liquid after adopting Al to replace crystallization under the temperature environment of 50-60 DEG C, after displacement 9-11h, obtains silver-colored tender crystalline mother solution;
5. to thiocarbamide in crystalline mother solution with urge propose agent content traditionally characterization processes detect, and the content adding thiocarbamide is 40-60g/l, the content proposing agent is urged to be after 4-7g/l, obtain the crystalline mother solution after adjustment, and the crystalline mother solution after adjustment is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. being the sulphuric acid soln of 50-60g/l by crystallized product and concentration, is 3-5 according to liquid-solid ratio, when adjustment pH value is 1-2, dissolves at 50-60 DEG C, obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. be placed in after temperature is the calcining furnace calcination processing 2-5h of 500-600 DEG C by adopting Cu displacement to obtain the continuous silver silk floss obtained of replace with Al of silver, then adopt concentration to be the acid solution of 200g/l, be 3-5 according to liquid-solid ratio, lixiviate 2-4h, obtains immersion liquid c and soaks slag c;
9. soak slag c and return continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, addition quantity of HCl mol ratio is HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, AgCl precipitation adopt reductive agent from normal temperature according to rate of warming be 5 DEG C/min heat reach 60-65 DEG C to temperature time, obtain Ag powder, namely complete the extraction of Ag in flotation of silver concentrate;
10. Cu is replaced the displaced liquid reduction or dry in silver-colored step, the extraction of Cu in flotation of silver concentrate can be completed.
2. the method for as claimed in claim 1 extraction and isolation Ag, Cu from flotation of silver concentrate, is characterized in that, it is one in urea, sodium lignosulfonate or two kinds of mixtures that agent is proposed in described urging.
3. the method for extraction and isolation Ag, Cu from flotation of silver concentrate as claimed in claim 2, it is characterized in that, described urge carry agent be urea and sodium lignosulfonate two kinds of mixtures time, the mol ratio of urea and sodium lignosulfonate is (2-4): (1-3).
4. the method for as claimed in claim 2 extraction and isolation Ag, Cu from flotation of silver concentrate, is characterized in that, described urging carry agent be urea and sodium lignosulfonate two kinds of mixtures time, the mol ratio of urea and sodium lignosulfonate is 3:2.
5. the method for extraction and isolation Ag, Cu from flotation of silver concentrate as claimed in claim 1, is characterized in that, described displaced liquid reduction adopts the reduction of Zn powder.
6. the method for extraction and isolation Ag, Cu from flotation of silver concentrate as claimed in claim 1, it is characterized in that, described reductive agent refers to ammoniacal liquor-hydrazine hydrate.
7. the method for as claimed in claim 1 extraction and isolation Ag, Cu from flotation of silver concentrate, is characterized in that, described acid solution is the one in sulfuric acid or nitric acid.
8. the method for extraction and isolation Ag, Cu from flotation of silver concentrate as claimed in claim 1, it is characterized in that, the reduction of described AgCl precipitation first adopts the ammoniacal liquor of 10% to carry out normal temperature washing to AgCl precipitation, the ammoniacal liquor of 20% is adopted to size mixing under normal temperature environment again, and stir, then adopting heat-up rate to be 5 DEG C/min when being warming up to 60-65 DEG C, constant temperature adds hydrazine hydrate, when the no longer generation of Ag precipitates in solution, stop adding of hydrazine hydrate.
9. the method for extraction and isolation Ag, Cu from flotation of silver concentrate as claimed in claim 1, is characterized in that, described silver silk floss calcining is that the silver cemented out by Al is continuous under the environment of 600 DEG C, after calcination processing 2h, adopting concentration to be the salpeter solution of 200g/l, is 4 according to liquid-solid ratio, lixiviate 4h; Described silver silk floss calcining is that the silver cemented out by Cu is continuous under the environment of 500 DEG C, and after calcination processing 5h, employing sulfuric acid concentration is 200g/l, is 5 according to liquid-solid ratio, lixiviate 2h.
10. the method for as claimed in claim 1 extraction and isolation Ag, Cu from flotation of silver concentrate, is characterized in that, the one in what described Al displacement silver adopted is Al powder or Al plate; One in what described Cu displacement silver adopted is Cu powder or Cu plate.
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| CN102690947A (en) * | 2012-05-24 | 2012-09-26 | 赤峰中色锌业有限公司 | Smelting process of silver concentrate |
| CN103215435A (en) * | 2013-04-27 | 2013-07-24 | 湖南水口山有色金属集团有限公司 | Method for comprehensively recycling zinc, copper, lead, gold, silver and sulfur from floatation silver concentrate |
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| CN102690947A (en) * | 2012-05-24 | 2012-09-26 | 赤峰中色锌业有限公司 | Smelting process of silver concentrate |
| CN103215435A (en) * | 2013-04-27 | 2013-07-24 | 湖南水口山有色金属集团有限公司 | Method for comprehensively recycling zinc, copper, lead, gold, silver and sulfur from floatation silver concentrate |
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