CN102943180B - Method for recycling gold and silver from silver separating residues of copper anode slime - Google Patents
Method for recycling gold and silver from silver separating residues of copper anode slime Download PDFInfo
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- CN102943180B CN102943180B CN201210475308.2A CN201210475308A CN102943180B CN 102943180 B CN102943180 B CN 102943180B CN 201210475308 A CN201210475308 A CN 201210475308A CN 102943180 B CN102943180 B CN 102943180B
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Abstract
The invention relates to a method for recycling gold and silver from waste residues and particularly relates to a method for recycling gold and silver from silver separating residues of copper anode slime. The method specifically includes that the silver separating residues of the copper anode slime and sodium thiosulfate are subjected to mixing and ball-milling to obtain a ball-milling material; the ball-milling material and a reaction solvent are filled in a hydrothermal reaction still for hydrothermal reaction; and thiourea dioxide is added into a hydrothermal solution obtained by filtering a hydrothermal product for reduction reaction to obtain coarse gold and silver powders. Compared with methods in prior art, the method has the advantages that by means of the ball-milling and the hydrothermal reaction, leaching rates of the gold and the silver are greatly improved, the process is simple and easy to achieve, and raw materials are common, cheap and pollution-free.
Description
Technical field
The present invention relates to reclaim the method for gold and silver in waste residue, particularly relate to the method for hydrometallurgic recovery silver separating residue of copper anode slime gold and silver.
Background technology
Dividing silver-colored slag is that copper anode mud extracts the recrement after the valuable elements such as precious metal gold and silver, platinum, palladium and copper, selenium, tellurium.Copper anode mud is in electrorefining process, the element and the various materials compositions that are insoluble to electrolytic solution higher than copper current potential, and its composition depends primarily on the technical qualification of composition, castability and the electrolysis of copper anode, and its productive rate is generally 0.2 ~ 0.8%; It contains Au, Ag, Cu, Pb, Se, Te, As, Sb, Bi, Ni, Fe, S, Sn, SiO conventionally
2, A1
2o
3, platinum metals and moisture.Derive from the anode sludge of copper sulfide concentrate, contain more Cu, Se, Ag, Pb, Te and a small amount of Au, Sb, Bi, As and gangue mineral, platinum metals is little; And the anode sludge that derives from copper-Ni sulphide mine contains more Cu, Ni, S, Se, precious metal is mainly platinum metals, and the content of Au, Ag, Pb is less; The 50-60% that divides the output capacity of silver-colored slag to be generally copper anode mud, produces the smeltery of 100,000 t electrolytic coppers per year for one, output anode sludge 750t left and right, and output is divided silver-colored slag 350-450t.The anode sludge that cupric electrolysis produces is containing higher Pb, Sn, and precious metal is mainly Ag, Au and platinum metals; Point silver-colored slag that precious metal obtains after extracting is except containing higher Pb, Sn, the about 10g/t of gold content, silver 200g/t to 2000g/t left and right, platinum palladium content is in 5g/t to 15g/t left and right, the content of precious metal than the precious metal ore generally exploited high several times to hundred times, so the recycling that this slag is made to further precious metal is very important.But than the anode sludge, point silver-colored slag bullion content is low, reclaims precious metal more difficult.
The domestic recycling of the gold and silver to point silver-colored slag research is few, some smeltery divides silver-colored slag to adopt oxygen bottom-blowing to send out dividing a silver-colored slag to carry out continuous oxidation-reduction smelting (patent application 200810049459.5), obtain precious metals containing lead and high lead slag, precious metals containing lead obtains precious metal alloys through refining, electrolysis obtains silver and gold, cause melting to pollute, and long flow path, the rate of recovery are low.So most of producers all temporarily stack point silver-colored slag on one side now, wait until further exploitation.Minority producer is sold some special precious metal returned enterprises and is processed recovery; carry out the extraction (patent application 90103200.X, 97105925.X, 200710303815.7) of some precious metal element; the recovery of this extensive style is with some valuable metal in waste slag; and in technique, do not consider environment protection, not only wasted resource but also caused new environmental pollution.
Cyanide process, as a kind of gold-leaching technology of maturation, for a long time by people are used, but because traditional cyanide process produces a large amount of cyanide wastewater, cause great harm to staff and environment, and the dissolution rate of gold is also slower, and the production cycle is long.Thio sulfate method has the features such as reagent is nontoxic, leaching agent consumption is little, cheap and easy to get, leaching velocity fast, the easy recovery of gold.There is O
2while existence, Sulfothiorine can form stable complex compound with gold:
4Au+8S
2O
3 2-+2H
2O+O
2=4Au(S
2O
3)
2 3-+4OH
-
When there being Cu in solution
2+, NH
3, S
2o
3 2-time, Sulfothiorine more easily forms stable complex compound with gold.
The method of Leaching of Silver mainly contains ammoniacal liquor lixiviation process and S-WAT lixiviation process, and they are mainly applicable to the situation that silver content is higher.Sulfothiorine and silver ions can form stable complex compound, silver chloride, silver sulfide and argent are had to good leaching effect, and under lower concentration of sodium thiosulfate, there is higher leaching yield, simultaneously the leaching velocity of thiosulphate is fast, leaching yield is high, nontoxic, low to other base metal leaching yield, therefore selectivity is good, be the leaching agent of good low-grade silver, it is applicable to leach Ag, Ag
2the silver that the various ways such as O, AgCl exists.
4Ag?+8S
2O
3 2-+2H
2O+O
2=4Ag(S
2O
3)
2 3-+4OH
-
Ag
2O+4S
2O
3 2-+H
2O=2Ag(S
2O
3)
2 3-+2OH
-
AgCl?+S
2O
3 2-=Ag(S
2O
3)
2 3-+Cl
-
Summary of the invention
Object of the present invention mainly solves gold and silver in silver separating residue of copper anode slime and reclaims problem, not only can ensure that efficient recovery divides the precious metal of the gold and silver in silver-colored slag, and processing technological flow is short, equipment is simple.
The method that silver separating residue of copper anode slime of the present invention reclaims gold and silver is as follows:
By design requirements, silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, wherein Sulfothiorine: silver separating residue of copper anode slime=1:10 ~ 3:10(mass ratio), Ball-milling Time is 1 ~ 3 hour, obtains ball milling material; Ball milling material and reaction solvent are packed into and in hydrothermal reaction kettle, carry out hydro-thermal reaction, wherein ball milling material: reaction solvent (mass ratio)=1:1 ~ 1:3, reaction solvent is made up of copper sulfate and ammonia aqueous solution, wherein concentration of copper sulfate is 3 ~ 8g/L, ammonia concn is: 50 ~ 100mL/L(20% ammoniacal liquor), ball milling material and reaction solvent account for 20 ~ 40% of whole reactor volume, and hydrothermal temperature is 140 ~ 180 DEG C, and the reaction times is 1 ~ 4 hour; Hydrothermal product is filtered and obtains hydro-thermal slag and hydro-thermal liquid, and hydro-thermal slag focuses on; In hydro-thermal liquid, add thiourea peroxide to carry out reduction reaction, wherein thiourea peroxide add-on is 5 ~ 10g/L, and reduction temperature is 30 ~ 60 DEG C, and the recovery time is 1 ~ 3 hour; Reduzate is filtered and obtains thick metal(lic)powder and the rear liquid of reduction, and after reduction, liquid focuses on.
Beneficial effect of the present invention is: compared with prior art, because the present invention has adopted ball milling and hydro-thermal reaction, greatly improve gold and silver leaching rate.The present invention has simple for process, the raw materials used feature such as more common and cheap, pollution-free.
Brief description of the drawings
Fig. 1 represents that silver separating residue of copper anode slime reclaims gold and silver process flow sheet
Embodiment
Embodiment 1
Silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, and wherein the mass ratio of silver separating residue of copper anode slime and Sulfothiorine is 10:1, and Ball-milling Time is 1 hour, obtains ball milling material; Ball milling material and reaction solvent are packed in hydrothermal reaction kettle, wherein the mass ratio of ball milling material and reaction solvent is 1:1, ball milling material and reaction solvent cumulative volume account for 20% of hydrothermal reaction kettle volume, hydrothermal temperature is 140 DEG C, reaction times is 1 hour, wherein reaction solvent is made up of copper sulfate and ammonia aqueous solution, and concentration of copper sulfate is 3g/L, and 20% ammonia concn is 50mL/L(20% ammoniacal liquor); Hydrothermal product is filtered and obtains hydro-thermal slag and hydro-thermal liquid, and hydro-thermal slag focuses on; In hydro-thermal liquid, add thiourea peroxide to carry out reduction reaction, the concentration that makes thiourea peroxide is 5g/L, and reduction temperature is 30 DEG C, and the recovery time is 1 hour; Reduzate is filtered and obtains thick metal(lic)powder and the rear liquid of reduction, and after reduction, liquid focuses on.Gold recovery 95.2%, the rate of recovery 97.3% of silver.
Embodiment 2
Silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, and wherein the mass ratio of silver separating residue of copper anode slime and Sulfothiorine is 10:3, and Ball-milling Time is 2 hours, obtains ball milling material; Ball milling material and reaction solvent are packed in hydrothermal reaction kettle, wherein the mass ratio of ball milling material and reaction solvent is 1:1.5, ball milling material and reaction solvent cumulative volume account for 25% of hydrothermal reaction kettle volume, hydrothermal temperature is 180 DEG C, reaction times is 4 hours, wherein reaction solvent is made up of copper sulfate and ammonia aqueous solution, and concentration of copper sulfate is 8g/L, and 20% ammonia concn is 100mL/L(20% ammoniacal liquor); Hydrothermal product is filtered and obtains hydro-thermal slag and hydro-thermal liquid, and hydro-thermal slag focuses on; In hydro-thermal liquid, add thiourea peroxide to carry out reduction reaction, the concentration that makes thiourea peroxide is 10g/L, and reduction temperature is 60 DEG C, and the recovery time is 3 hours; Reduzate is filtered and obtains thick metal(lic)powder and the rear liquid of reduction, and after reduction, liquid focuses on.Gold recovery 95.5%, the rate of recovery 98.1% of silver.
Embodiment 3
Silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, and wherein the mass ratio of silver separating residue of copper anode slime and Sulfothiorine is 10:2, and Ball-milling Time is 1.5 hours, obtains ball milling material; Ball milling material and reaction solvent are packed in hydrothermal reaction kettle, wherein the mass ratio of ball milling material and reaction solvent is 1:3, ball milling material and reaction solvent cumulative volume account for 40% of hydrothermal reaction kettle volume, hydrothermal temperature is 160 DEG C, reaction times is 2 hours, wherein reaction solvent is made up of copper sulfate and ammonia aqueous solution, and concentration of copper sulfate is 5g/L, and 20% ammonia concn is 70mL/L(20% ammoniacal liquor); Hydrothermal product is filtered and obtains hydro-thermal slag and hydro-thermal liquid, and hydro-thermal slag focuses on; In hydro-thermal liquid, add thiourea peroxide to carry out reduction reaction, the concentration that makes thiourea peroxide is 8g/L, and reduction temperature is 40 DEG C, and the recovery time is 2 hours; Reduzate is filtered and obtains thick metal(lic)powder and the rear liquid of reduction, and after reduction, liquid focuses on.Gold recovery 95.1%, the rate of recovery 98.4% of silver.
Embodiment 4
Silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, and wherein the mass ratio of silver separating residue of copper anode slime and Sulfothiorine is 10:1.5, and Ball-milling Time is 3 hours, obtains ball milling material; Ball milling material and reaction solvent are packed in hydrothermal reaction kettle, wherein the mass ratio of ball milling material and reaction solvent is 1:2, ball milling material and reaction solvent cumulative volume account for 30% of hydrothermal reaction kettle volume, hydrothermal temperature is 170 DEG C, reaction times is 2.5 hours, wherein reaction solvent is made up of copper sulfate and ammonia aqueous solution, and concentration of copper sulfate is 6g/L, and 20% ammonia concn is 85mL/L(20% ammoniacal liquor); Hydrothermal product is filtered and obtains hydro-thermal slag and hydro-thermal liquid, and hydro-thermal slag focuses on; In hydro-thermal liquid, add thiourea peroxide to carry out reduction reaction, the concentration that makes thiourea peroxide is 7g/L, and reduction temperature is 50 DEG C, and the reaction times is 2.5 hours; Reduzate is filtered and obtains thick metal(lic)powder and the rear liquid of reduction, and after reduction, liquid focuses on.Gold recovery 97.1%, the rate of recovery 98.6% of silver.
Claims (2)
1. the method that silver separating residue of copper anode slime gold and silver reclaims, is characterized in that, described method steps is as follows:
(1) silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, wherein Sulfothiorine: silver separating residue of copper anode slime mass ratio=1:10～3:10, Ball-milling Time is 1～3 hour, obtains ball milling material;
(2) ball milling material and reaction solvent are packed into and in hydrothermal reaction kettle, carry out hydro-thermal reaction, wherein ball milling material: reaction solvent mass ratio=1:1～1:3, reaction solvent is made up of copper sulfate and ammonia aqueous solution, wherein concentration of copper sulfate is 3～8g/L, ammonia concn is: 50～100mL/L, described ammoniacal liquor is 20% ammoniacal liquor, and hydrothermal temperature is 140～180 DEG C, and the reaction times is 1～4 hour;
(3) hydrothermal product is filtered and obtains hydro-thermal slag and hydro-thermal liquid, hydro-thermal slag focuses on; In hydro-thermal liquid, add thiourea peroxide to carry out reduction reaction, wherein thiourea peroxide add-on is 5～10g/L, and reduction temperature is 30～60 DEG C, and the recovery time is 1～3 hour;
(4) reduzate is filtered and obtain thick metal(lic)powder and the rear liquid of reduction, after reduction, liquid focuses on.
2. method according to claim 1, is characterized in that: in described step (2), ball milling material and reaction solvent account for 20～40% of whole reactor volume.
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| CN103194610B (en) * | 2013-04-24 | 2014-10-22 | 湖北鑫荣矿业有限公司 | Method for extracting gold from silver separating residues in nonferrous metal exploitation |
| CN103320624B (en) * | 2013-07-05 | 2014-07-30 | 昆明理工大学 | Method for selectively extracting gold and silver from copper anode slime |
| RO129874B1 (en) * | 2014-04-30 | 2018-05-30 | Florean Victor | Process for extraction of gold and silver from ores and mining by-products |
| 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 |
| CN108034825B (en) * | 2017-12-22 | 2019-07-19 | 中国科学院过程工程研究所 | The method that wet process extracts gold and silver from the earth of positive pole |
| CN112831657A (en) * | 2019-11-25 | 2021-05-25 | 荆门市格林美新材料有限公司 | Method for extracting gold from copper anode mud |
| CN114058857A (en) * | 2021-11-12 | 2022-02-18 | 水口山有色金属有限责任公司 | Method for recovering lead and manganese from electrolytic manganese anode slime |
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| CN101555550A (en) * | 2009-05-22 | 2009-10-14 | 北京科技大学 | Method for recycling lead-tin in silver separating residue of copper anode slime of circuit board |
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| CN101555550A (en) * | 2009-05-22 | 2009-10-14 | 北京科技大学 | Method for recycling lead-tin in silver separating residue of copper anode slime of circuit board |
Non-Patent Citations (4)
| Title |
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| 张钦发等.用硫代硫酸钠从分银渣中提取银.《贵金属》.2003,第24卷(第1期),第5-9页. |
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| 曾秀琼.二氧化硫脲还原[ Ag( S2O3) 2 ] 3- 以沉析银的研究.《贵金属》.2001,第22卷(第2期),第16-19页. * |
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Effective date of registration: 20160901 Address after: 100083 Haidian District, Xueyuan Road, No. 30, Patentee after: University of Science and Technology Beijing Patentee after: Shangrao Zhiyuan Environmental Protection Technology Co., Ltd. Address before: 100083 Haidian District, Xueyuan Road, No. 30, Patentee before: University of Science and Technology Beijing |