CN104032145A - Method for extracting and separating Ag and Cu from flotation silver concentrate - Google Patents
Method for extracting and separating Ag and Cu from flotation silver concentrate Download PDFInfo
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Abstract
The invention relates to the technical field of hydrometallurgy and particularly relates to a method for extracting and separating Ag and Cu from flotation silver concentrate. The method comprises the steps: carrying out combined cycle leaching by using thiourea and urea, cooling and crystallizing thiourea Cu of which the content of Cu is above 15%, the content of Ag is about 2%, the content of Pb is 0.04%, and the content of Zn is about 1%; replacing silver cotton with an Al plate, and regenerating thiourea; and then supplementing thiourea and a catalytic leaching agent, returning to the secondary thiourea leaching; carrying out cycle leaching for 3-4 times to generate saturated crystals of thiourea Cu, dissolving saturated crystals of thiourea Cu with diluted H2SO4, then replacing Ag with Cu, replacing Cu with Zn powder or carrying out evaporative crystallization to obtain CuSO4.5H2O, replacing silver cotton in the crystallization solution with A1, and mixing the Al-replaced silver cotton with Cu-replaced silver cotton, calcinating at 500 DEG C, leaching with H2SO4 or HNO3; precipitating Ag in the leaching solution with HCl to obtain AgCl, and then reducing AgCl with a mixture of ammonia and hydrazine to obtain Ag powder of which the purity is 99.95%, and then casting Ag powder into a Ag ingot.
Description
Technical field
The present invention relates to technical field of wet metallurgy, especially a kind of method that separates Ag, Cu of extracting from flotation of silver concentrate.
Background technology
Flotation of silver concentrate is generally by the slag that soaks that adopts butylamine black powder or butyl xanthate lixiviate left behind from zinc leaching residue or other argentiferous leached muds, its contain the about 2000g/t of Ag above, containing Cu more than approximately 2%, containing Zn more than approximately 20%, contain Pb more than approximately 8%, contain more than about S18%, as can be seen here, in flotation of silver concentrate, also contain a large amount of Ag, Cu, Zn, Pb raw material; Traditional extracting method has for this reason: the extraction that combines with thiocarbamide lixiviate of pyrometallurgical smelting, roast reduction process or pyrometallurgical smelting; Wherein pyrometallurgical smelting is that employing high temperature is added Cu or Pb carries out fire reduction melting, then carries out electrolysis Cu or Pb, and reclaims silver-colored method from the anode sludge, and this method facility investment is large, technical process is long, production cost is high; Roast reduction process is first flotation of silver concentrate to be placed in to 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, in the time of oxidizing roasting, produces a large amount of SO2 flue gases, causes environmental pollution; Pyrometallurgical smelting with the extracting method that thiocarbamide lixiviate combines is: flotation of silver concentrate is placed in to thiourea solution, first uses zinc dust precipitation Ag, obtain Ag silk floss, then use zinc dust precipitation Cu; And by continuous Ag calcining, 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 cupellation obtain 99% thick Ag again electrolysis obtain 99.15 or 99.97% smart Ag, although this method has reduced facility investment, shortened technical process, its energy consumption is larger, production cost is higher.
" difficulty is soaked independent silver deposit flotation of silver concentrate and extracted silver-colored and golden method " that be CN95119869.6 as the patent No. be CN201310186779.6 " extracting method of silver in a kind of agglomeration for iron mine smoke dust " and the patent No. is the silver-colored extraction 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 costs.But all also comparatively undesirable.
Summary of the invention
In order to solve the above-mentioned technical problem existing in prior art, the invention provides a kind of method that separates Ag, Cu of extracting from flotation of silver concentrate, having silver products quality can be ensured, the purity of the product obtaining is high, thiocarbamide loss is little, avoids environmental pollution, and the energy consumption while also having avoided argentiferous precious metals containing lead to adopt pyrometallurgical smelting is large, silver loss is large, the feature that cost is high.
Specifically be achieved by the following technical programs:
From flotation of silver concentrate, extract a method that separates Ag, Cu, comprise the following steps:
(1) leach liquor preparation:
Choose thiocarbamide and propose agent and prepare leach liquor with urging, wherein in leach liquor, be 40-60g/l, carry agent 4-7g/l containing urging containing thiocarbamide;
(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 filter to obtain and soak slag a and immersion liquid a;
2. will soak slag a is 3-5 according to liquid-solid ratio again, is placed in temperature and is the thiocarbamide of 80-90 DEG C and urge and carry agent leach liquor, and secondary lixiviate 4-5h, filters to obtain and soaks slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate and mixes composition leach liquor with a leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. to be cooled to temperature be≤25 DEG C of crystallization treatment to immersion liquid a, 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 the content of proposing agent to detect according to traditional detection technique, and the content that adds thiocarbamide is 40-60g/l, after urging the content of proposing agent to be 4-7g/l, obtain the crystalline mother solution after adjusting, and crystalline mother solution after adjusting is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. the sulphuric acid soln that is 50-60g/l by crystallized product and concentration, is 3-5 according to liquid-solid ratio, when adjusting pH value and being 1-2, at 50-60 DEG C, dissolves, and obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. by after adopting Cu displacement to obtain the continuous silver silk floss obtaining with Al displacement of silver to be placed in temperature and to be the calcining furnace calcination processing 2-5h of 500-600 DEG C, then to adopt concentration be the acid solution of 200g/l, is 3-5 according to liquid-solid ratio, and lixiviate 2-4h, obtains immersion liquid c and soak slag c;
9. soak slag c and return to continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, HCl add-on mol ratio is that HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, and it is that 5 DEG C/min heats while reaching 60-65 DEG C to temperature from normal temperature according to rate of warming that AgCl precipitation adopts reductive agent, obtains Ag powder, completes the extraction of Ag in flotation of silver concentrate;
10. Cu replaced to the displaced liquid reduction in silver-colored step or be dried, can complete the extraction of Cu in flotation of silver concentrate.
Described urge that to propose agent be a kind of or two kinds of mixtures in urea, sodium lignosulfonate.
Described urging when proposing agent and being urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is (2-4): (1-3).
Described urging when proposing agent and being urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is 3:2.
Described displaced liquid reduction is to adopt 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 is first to adopt 10% ammoniacal liquor to carry out normal temperature washing to AgCl precipitation, adopt again 20% ammoniacal liquor to size mixing under normal temperature environment, and stir, adopting heat-up rate is that 5 DEG C/min is while 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.
The continuous calcining of described silver be silver silk floss that AL is cemented out under the environment of 600 DEG C, after calcination processing 2h, adopt the salpeter solution that concentration is 200g/l, be 4 according to liquid-solid ratio, lixiviate 4h;
The continuous calcining of described silver be silver silk floss that Cu is cemented out under the environment of 500 DEG C, after calcination processing 5h, employing sulfuric acid concentration is 200g/l, is 5 according to liquid-solid ratio, lixiviate 2h.
What described Al displacement silver adopted is the one in Al powder or Al plate;
What described Cu displacement silver adopted is the one in Cu powder or Cu plate.
Compared with prior art, technique effect of the present invention is embodied in:
1. by thiocarbamide leaches, in thiourea solution, add 10% urea, and leaching crystalline mother solution is carried out to circulating leaching, make the thiocarbamide copper in flotation concentrate obtain enrichment, silver in flotation of silver concentrate and the rate of recovery of copper are improved, the silver-colored rate of recovery is reached more than 99%, and the rate of recovery of copper reaches more than 83%, the pollution of the flotation of silver concentrate slag that has reduced argentiferous and copper to environment.
2. adopting A1 displacement Ag to obtain the continuous thiocarbamide regeneration quality that makes of Ag by the mechanism of utilizing A1 and thiocarbamide not to produce complexing action is guaranteed; Overcome thiocarbamide Zn crystallization and blocked pipeline, reduced the loss of thiocarbamide, reduced production cost.
3. by after Ag silk floss is calcined under the environment of 500 DEG C of left and right; Adopt acidleach, AgCl precipitation, the technique of ammoniacal liquor and hydrazine hydrate reduction metal A g powder, the metal A g powder that obtains containing 99.95% purity is again 1000～1100 DEG C of foundings, and it is more than 95% making founding rate; Overcome employing pyrometallurgical smelting containing Ag precious metals containing lead, then carried out cupellation, when electrolytic refining metal Ag, the long flow path having, 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, technical scheme of the present invention is done to further restriction, but claimed scope is not only confined to done description.
Embodiment 1
From flotation of silver concentrate, extract a method that separates Ag, Cu, comprise the following steps:
(1) leach liquor preparation:
Choose thiocarbamide and propose agent and prepare leach liquor with urging, wherein in leach liquor, be 40g/l, carry agent 4g/l containing urging containing thiocarbamide;
(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 filter to obtain and soak slag a and immersion liquid a;
2. will soak slag a is 3 according to liquid-solid ratio again, is placed in temperature and is the thiocarbamide of 80 DEG C and urge and carry agent leach liquor, and secondary lixiviate 4h, filters to obtain and soaks slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate and mixes composition leach liquor with a leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. to be cooled to temperature be 25 DEG C of crystallization treatment to immersion liquid a, 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 the content of proposing agent to detect according to traditional detection technique, and the content that adds thiocarbamide is 40g/l, after urging the content of proposing agent to be 4g/l, obtain the crystalline mother solution after adjusting, and crystalline mother solution after adjusting is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. the sulphuric acid soln that is 50g/l by crystallized product and concentration, is 3 according to liquid-solid ratio, and adjusting pH value is 1 o'clock, at 50 DEG C, dissolves, and obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. by after adopting Cu displacement to obtain the continuous silver silk floss obtaining with Al displacement of silver to be placed in temperature and to be the calcining furnace calcination processing 2h of 500 DEG C, then to adopt concentration be the acid solution of 200g/l, is 3 according to liquid-solid ratio, and lixiviate 2h, obtains immersion liquid c and soak slag c;
9. soak slag c and return to continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, HCl add-on mol ratio is that HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, and it is that 5 DEG C/min heats while reaching 60 DEG C to temperature from normal temperature according to rate of warming that AgCl precipitation adopts reductive agent, obtains Ag powder, completes the extraction of Ag in flotation of silver concentrate;
10. Cu replaced to the displaced liquid reduction in silver-colored step or be dried, can complete the extraction of Cu in flotation of silver concentrate.
Described urge that to propose agent be urea.
Described displaced liquid reduction is to adopt 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 is first to adopt 10% ammoniacal liquor to carry out normal temperature washing to AgCl precipitation, adopt again 20% ammoniacal liquor to size mixing under normal temperature environment, and stir, adopting heat-up rate is that 5 DEG C/min is while 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
From flotation of silver concentrate, extract a method that separates Ag, Cu, comprise the following steps:
(1) leach liquor preparation:
Choose thiocarbamide and propose agent and prepare leach liquor with urging, wherein in leach liquor, be 60g/l, carry agent 7g/l containing urging containing thiocarbamide;
(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 filter to obtain and soak slag a and immersion liquid a;
2. will soak slag a is 5 according to liquid-solid ratio again, is placed in temperature and is the thiocarbamide of 90 DEG C and urge and carry agent leach liquor, and secondary lixiviate 5h, filters to obtain and soaks slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate and mixes composition leach liquor with a leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. to be cooled to temperature be 20 DEG C of crystallization treatment to immersion liquid a, 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 the content of proposing agent to detect according to traditional detection technique, and the content that adds thiocarbamide is 60g/l, after urging the content of proposing agent to be 7g/l, obtain the crystalline mother solution after adjusting, and crystalline mother solution after adjusting is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. the sulphuric acid soln that is 60g/l by crystallized product and concentration, is 5 according to liquid-solid ratio, and adjusting pH value is 2 o'clock, at 60 DEG C, dissolves, and obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. by after adopting Cu displacement to obtain the continuous silver silk floss obtaining with Al displacement of silver to be placed in temperature and to be the calcining furnace calcination processing 5h of 600 DEG C, then to adopt concentration be the acid solution of 200g/l, is 5 according to liquid-solid ratio, and lixiviate 4h, obtains immersion liquid c and soak slag c;
9. soak slag c and return to continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, HCl add-on mol ratio is that HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, and it is that 5 DEG C/min heats while reaching 65 DEG C to temperature from normal temperature according to rate of warming that AgCl precipitation adopts reductive agent, obtains Ag powder, completes the extraction of Ag in flotation of silver concentrate;
10. Cu replaced to the displaced liquid reduction in silver-colored step or be dried, can complete the extraction of Cu in flotation of silver concentrate.
Described urge that to propose agent be sodium lignosulfonate.
Described displaced liquid reduction is to adopt 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 is first to adopt 10% ammoniacal liquor to carry out normal temperature washing to AgCl precipitation, adopt again 20% ammoniacal liquor to size mixing under normal temperature environment, and stir, adopting heat-up rate is that 5 DEG C/min is while 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
From flotation of silver concentrate, extract a method that separates Ag, Cu, comprise the following steps:
(1) leach liquor preparation:
Choose thiocarbamide and propose agent and prepare leach liquor with urging, wherein in leach liquor, be 50g/l, carry agent 5.5g/l containing urging containing thiocarbamide;
(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 filter to obtain and soak slag a and immersion liquid a;
2. will soak slag a is 4 according to liquid-solid ratio again, is placed in temperature and is the thiocarbamide of 85 DEG C and urge and carry agent leach liquor, and secondary lixiviate 4.5h, filters to obtain and soaks slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate and mixes composition leach liquor with a leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. to be cooled to temperature be 15 DEG C of crystallization treatment to immersion liquid a, 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 the content of proposing agent to detect according to traditional detection technique, and the content that adds thiocarbamide is 50g/l, after urging the content of proposing agent to be 5.5g/l, obtain the crystalline mother solution after adjusting, and crystalline mother solution after adjusting is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. the sulphuric acid soln that is 55g/l by crystallized product and concentration, is 4 according to liquid-solid ratio, and adjusting pH value is 1.5 o'clock, at 55 DEG C, dissolves, and obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. by after adopting Cu displacement to obtain the continuous silver silk floss obtaining with Al displacement of silver to be placed in temperature and to be the calcining furnace calcination processing 3.5h of 550 DEG C, then to adopt concentration be the acid solution of 200g/l, is 4 according to liquid-solid ratio, and lixiviate 3h, obtains immersion liquid c and soak slag c;
9. soak slag c and return to continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, HCl add-on mol ratio is that HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, and it is that 5 DEG C/min heats while reaching 63 DEG C to temperature from normal temperature according to rate of warming that AgCl precipitation adopts reductive agent, obtains Ag powder, completes the extraction of Ag in flotation of silver concentrate;
10. Cu replaced to the displaced liquid reduction in silver-colored step or be dried, can complete the extraction of Cu in flotation of silver concentrate.
Described urge that to propose agent be urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is 2:1.
Described displaced liquid reduction is to adopt 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 is first to adopt 10% ammoniacal liquor to carry out normal temperature washing to AgCl precipitation, adopt again 20% ammoniacal liquor to size mixing under normal temperature environment, and stir, adopting heat-up rate is that 5 DEG C/min is while 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
From flotation of silver concentrate, extract the method for Ag, Cu of separation, on the basis of embodiment 1, when described urging proposed agent and be urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is 4:3.
The continuous calcining of described silver be silver silk floss that AL is cemented out under the environment of 600 DEG C, after calcination processing 2h, adopt the salpeter solution that concentration is 200g/l, be 4 according to liquid-solid ratio, lixiviate 4h;
The continuous calcining of described silver be silver silk floss that Cu is cemented out under the environment of 500 DEG C, 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
From flotation of silver concentrate, extract the method for Ag, Cu of separation, on the basis of embodiment 2, when described urging proposed agent and be urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is 3:2.
The continuous calcining of described silver be silver silk floss that AL is cemented out under the environment of 600 DEG C, after calcination processing 2h, adopt the salpeter solution that concentration is 200g/l, be 4 according to liquid-solid ratio, lixiviate 4h;
The continuous calcining of described silver be silver silk floss that Cu is cemented out under the environment of 500 DEG C, 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.
Concrete grammar and step that 6 technological experiment chamber interior of embodiment are carried out
From flotation of silver concentrate, extract a method that separates Ag, Cu,
(1) oxygenant adds impact experiment and the extracting efficiency experiment that repeatedly circulates: get flotation of silver concentrate material 600, detect containing Ag2580g/t Zn23.62%, Pb8.12%, Cu1.51%, S18.1%; Adopt H
2sO
450g/L, thiocarbamide 60g/L, urea 7g/L, hydrogen peroxide 20ml, is 85 DEG C in temperature, is mixed with leach liquor; And flotation concentrate is placed in to leach liquor, carry out circulating leaching twice, 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, without impact, then leached mud and leach liquor are carried out to circulating leaching three times for silver-colored leaching yield, the thiocarbamide of 10g/L is pressed in the leaching for the second time of each circulation, 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 fluid of the Leaching In Thiourea Solutions for the first time 1000ml of circulating leaching be cooled to 25 DEG C, liquid after the red crystallization 20.5g of output and crystallization, detection draws: respectively containing Cu15.01%, Ag1.98%, Pb0.04%, Zn1.2%; After 500 DEG C of calcinations of this crystallization, containing Ag3.8%, Cu28.5%, uses rare H
2sO
4, adjusting 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, filter silver-colored silk floss, obtain liquid and silver silk floss; Vaporised liquid again, obtains CuSO
4.5H
2o;
(3) extract the Ag in flotation concentrate: by step 2) shown in after crystallization liquid carry out the displacement of Ag with aluminium sheet at 70 DEG C, 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 is continuous containing Ag54%; Displaced liquid is returned and is carried out circulating leaching after adding by 10g/L thiocarbamide and 3g/L urea, and detection draws: the leaching yield of the 4th circulation A g is 93.34%;
(4) reduction of Ag: by step 3) Gu shown in Ag silk floss after 2 hours, press liquid /=4 with HNO3 600 DEG C of calcinings, 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 in the time that Ag has not been leached, Pb, Zn, Cu are leached less; In this leach liquor, add HCl deposit A gCl by HCl/Ag=1.1, deposition rate 99.99%, AgCl first adds 10% ammonia scrubbing, adding 20% ammoniacal liquor sizes mixing and stirs again, heat to 60 DEG C and add hydrazine hydrate complete to precipitin reaction, the reduction ratio of Ag is that 99%, Ag opaque amount is more than 99.95%; The Ag that ammonia scrubbing liquid water and hydrazine reduce wherein obtains Ag powder containing Ag96.3%, and Ag powder obtains 99.95%Ag ingot 1000 DEG C of foundings, founding rate 95.93%.
As can be seen here, the Cu and the Ag that are undertaken in flotation of silver concentrate by the concrete experimental technique of the experiment in embodiment 6 extract, visible needs in technique adds oxygenant first the material in flotation of silver concentrate slag to be carried out to oxidizing reaction, and oxygenant whether add extraction yield for Ag without any impact; But simple thiocarbamide carries out extraction process and combines with urea with thiocarbamide that to carry out extracting efficiency and the leaching yield of lixiviate extraction process all more excellent for the leach liquor of composition; And through circulating leaching liquid repeatedly or soak slag and extract and leach, improved the extraction rate to the silver in flotation of silver concentrate, copper, improved extraction rate, reduced cost recovery, immersion liquid recycles, and has reduced environmental pollution; Metallic object calcining, has avoided 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 only limits to the concrete operation method of technical scheme of the present invention be further elaborated and understand; can not be understood to the further restriction to technical scheme of the present invention; 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. from flotation of silver concentrate, extract a method that separates Ag, Cu, it is characterized in that, comprise the following steps:
(1) leach liquor preparation: choose thiocarbamide and propose agent and prepare leach liquor with urging, be wherein 40-60g/l, carry agent 4-7g/l containing urging containing thiocarbamide in leach liquor;
(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 filter to obtain and soak slag a and immersion liquid a;
2. will soak slag a is 3-5 according to liquid-solid ratio again, is placed in temperature and is the thiocarbamide of 80-90 DEG C and urge and carry agent leach liquor, and secondary lixiviate 4-5h, filters to obtain and soaks slag b and immersion liquid b;
3. immersion liquid b returns in a lixiviate and mixes composition leach liquor with a leach liquor, continues the lixiviate of circulation flotation of silver concentrate;
4. to be cooled to temperature be≤25 DEG C of crystallization treatment to immersion liquid a, 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 the content of proposing agent to detect according to traditional detection technique, and the content that adds thiocarbamide is 40-60g/l, after urging the content of proposing agent to be 4-7g/l, obtain the crystalline mother solution after adjusting, and crystalline mother solution after adjusting is placed in secondary vat liquor and carries out secondary lixiviate as secondary vat liquor;
6. the sulphuric acid soln that is 50-60g/l by crystallized product and concentration, is 3-5 according to liquid-solid ratio, when adjusting pH value and being 1-2, at 50-60 DEG C, dissolves, and obtains xln solution;
7. in xln solution, add Cu displacement silver, obtain silver-colored tender displaced liquid;
8. by after adopting Cu displacement to obtain the continuous silver silk floss obtaining with Al displacement of silver to be placed in temperature and to be the calcining furnace calcination processing 2-5h of 500-600 DEG C, then to adopt concentration be the acid solution of 200g/l, is 3-5 according to liquid-solid ratio, and lixiviate 2-4h, obtains immersion liquid c and soak slag c;
9. soak slag c and return to continuation calcining in calcining furnace, circulation lixiviate; In immersion liquid c, add HCl, HCl add-on mol ratio is that HCl/Ag is 1.1, obtains AgCl precipitation and filtrate; Filtrate returning adds in immersion liquid c, and it is that 5 DEG C/min heats while reaching 60-65 DEG C to temperature from normal temperature according to rate of warming that AgCl precipitation adopts reductive agent, obtains Ag powder, completes the extraction of Ag in flotation of silver concentrate;
10. Cu replaced to the displaced liquid reduction in silver-colored step or be dried, can complete the extraction of Cu in flotation of silver concentrate.
2. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 1, is characterized in that, it is a kind of or two kinds of mixtures in urea, sodium lignosulfonate that agent is proposed in described urging.
3. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 2, it is characterized in that, described urging when proposing agent and being urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is (2-4): (1-3).
4. the method for Ag, Cu of separation of extracting from flotation of silver concentrate as claimed in claim 2, is characterized in that, when described urging proposed agent and be urea and two kinds of mixtures of sodium lignosulfonate, the mol ratio of urea and sodium lignosulfonate is 3:2.
5. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 1, is characterized in that, described displaced liquid reduction is to adopt the reduction of Zn powder.
6. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 1, is characterized in that, described reductive agent refers to ammoniacal liquor-hydrazine hydrate.
7. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 1, is characterized in that, described acid solution is the one in sulfuric acid or nitric acid.
8. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 1, it is characterized in that, the reduction of described AgCl precipitation is first to adopt 10% ammoniacal liquor to carry out normal temperature washing to AgCl precipitation, adopt again 20% ammoniacal liquor to size mixing under normal temperature environment, and stir, then to adopt heat-up rate be 5 DEG C/min while 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 Ag, Cu of separation of extracting from flotation of silver concentrate as claimed in claim 1, is characterized in that, the continuous calcining of described silver is that silver silk floss that AL is cemented out is under the environment of 600 DEG C, after calcination processing 2h, adopting the salpeter solution that concentration is 200g/l, is 4 according to liquid-solid ratio, lixiviate 4h; The continuous calcining of described silver be silver silk floss that Cu is cemented out under the environment of 500 DEG C, after calcination processing 5h, employing sulfuric acid concentration is 200g/l, is 5 according to liquid-solid ratio, lixiviate 2h.
10. the method that separates Ag, Cu of extracting from flotation of silver concentrate as claimed in claim 1, is characterized in that, what described Al displacement silver adopted is the one in Al powder or Al plate; What described Cu displacement silver adopted is the one in Cu powder or Cu plate.
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Cited By (3)
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| CN106048659A (en) * | 2016-08-18 | 2016-10-26 | 紫金矿业集团股份有限公司 | Spent solution treatment method of silver electrolyte |
| CN106702166A (en) * | 2017-02-06 | 2017-05-24 | 温州中希电工合金有限公司 | Method for recycling silver in high oil-bearing sludge |
| CN111718383A (en) * | 2019-03-18 | 2020-09-29 | 中国科学院福建物质结构研究所 | [Ag(NH3)2]6@Ti4L6Molecular cage crystalline substance and preparation method and application thereof |
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| CN106048659A (en) * | 2016-08-18 | 2016-10-26 | 紫金矿业集团股份有限公司 | Spent solution treatment method of silver electrolyte |
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| CN111718383A (en) * | 2019-03-18 | 2020-09-29 | 中国科学院福建物质结构研究所 | [Ag(NH3)2]6@Ti4L6Molecular cage crystalline substance and preparation method and application thereof |
| CN111718383B (en) * | 2019-03-18 | 2021-09-21 | 中国科学院福建物质结构研究所 | [Ag(NH3)2]6@Ti4L6Molecular cage crystalline substance and preparation method and application thereof |
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