CN103966456B - A kind of method from silver separating residue of copper anode slime comprehensively recovering valuable metal - Google Patents
A kind of method from silver separating residue of copper anode slime comprehensively recovering valuable metal Download PDFInfo
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Abstract
The present invention relates to silver separating residue of copper anode slime reutilization technology, particularly a kind of method from silver separating residue of copper anode slime comprehensively recovering valuable metal.The present invention first will divide silver-colored slag to carry out hot acid leaching, filter to obtain the hot acid leach liquor of argentiferous and barium, and stanniferous and plumbous hot acid leached mud.Hot acid leach liquor dilute with water, filters the precipitation nitric acid dissolve obtained, filters to obtain barium sulfate precipitate and silver nitrate solution; Solution obtains silver powder through reduction.Hot acid leached mud leaches through acid villaumite, filters to obtain chloride leaching solution and villaumite leached mud; Chloride leaching solution separates out lead chloride through crystallisation by cooling, and villaumite leached mud obtains sodium stannate through alkali fusion, water logging, evaporative crystallization.The present invention is by the whole efficient recovery of valuable metal higher for content in point silver-colored slag, and plumbous, silver, tin and barium the rate of recovery reaches more than 97%, 92%, 90% and 95% respectively; Have technique simple, without " three wastes " discharge, metal recovery rate high, be applicable to large-scale commercial production.
Description
Technical field
The present invention relates to silver separating residue of copper anode slime reutilization technology, particularly a kind of method from silver separating residue of copper anode slime comprehensively recovering valuable metal.
Background technology
Point silver-colored slag is the recrement of copper anode mud after extracting the valuable metals such as precious metal gold and silver, platinum, palladium and copper, selenium, tellurium, and main component is platinum, the palladium of tin, lead, barium, silver and a small amount of gold and trace, has very high comprehensive reutilization value.
Current, few to valuable metal recovery research on utilization in point silver-colored slag, each smeltery is many will divide silver-colored slag to return pyrometallurgical smelting stove (application number: 200810049459.5), add Charge Treatment, and tin, lead is failed to open a way and is reclaimed, continuous accumulation, likely affect cupric electrolysis operation, minority sells precious metal returned enterprise, but also only focus on gold in point silver-colored slag, recovery (the patent application 90103200.X of silver, 97105925.X, 200710303815.7, 201010184502.6, 201110092626.6, 201210475308.2, 201310245462.5, 201310144214.1), cause the waste of other valuable metals.Patent application 200910084613.7 discloses a kind of method that silver separating residue of copper anode slime of circuit board reclaims slicker solder, patent application 201110292654.2 discloses a kind of method producing Babbitt metal from silver separating residue of copper anode slime, these methods relate to recovery that is plumbous in point silver-colored slag and tin, but mainly for silver separating residue of copper anode slime of circuit board.Different from silver separating residue of copper anode slime of circuit board, the anode sludge obtained from copper-sulphide ores or composition brass smelting process divides silver-colored slag except containing except more lead, silver and tin, containing the barium of about 30%, these barium exist with barium sulfate form, be wrapped in the valuable metals such as a large amount of tin, silver, bring very large difficulty to comprehensively recovering valuable metal from point silver-colored slag.
Summary of the invention
The object of this invention is to provide a kind of method from silver separating residue of copper anode slime comprehensively recovering valuable metal, can by valuable metal higher for content in silver separating residue of copper anode slime whole efficient recovery.
For achieving the above object, the present invention will divide silver-colored slag first to carry out hot acid leaching, and silver and barium are leached and enter hot acid leach liquor, tin and lead are stayed in hot acid leached mud; After hot acid leach liquor dilute with water, barium precipitates with Sulfuric acid disilver salt form with barium sulfate form, silver; Precipitation is after nitric acid dissolve, and barium is stayed in precipitation, and silver then enters solution with Silver Nitrate form, after reduction, obtain silver powder; Hot acid leached mud is after acid villaumite leaches, and lead enters chloride leaching solution with lead chloride form, and after crystallisation by cooling, separate out lead chloride crystallization, mother liquor returns villaumite and leaches; Villaumite leached mud is after alkali fusion, water logging, evaporative crystallization, and obtain sodium stannate crystallization, crystalline mother solution returns alkali fusion.
The technological process that the present invention is concrete and processing parameter as follows:
A, silver separating residue of copper anode slime is put into steel basin, adds the vitriol oil and carry out hot acid leaching, after filtration hot acid leached mud and hot acid leach liquor; Extract technology condition is: liquid-solid mass ratio is 2:1 ~ 10:1, and temperature is 200 ~ 500 DEG C, and the time is 5 ~ 60 minutes;
B, by step A hot acid leach liquor dilute with water, water consumption is 10% ~ 50% of hot acid leach liquor volume, after filtration diluent and precipitation, diluent returns copper anode mud pretreatment process;
C, the precipitation that step B water logging obtains is put into steel basin, add 16mol/L nitric acid dissolve, liquid-solid mass ratio is 1:1 ~ 3:1, after filtration barium sulfate precipitate and silver nitrate solution;
D, the silver nitrate solution hydrazine hydrate (N that step C is obtained
2h
4h
2o) carry out reduction at normal temperatures and obtain silver powder, hydrazine hydrate consumption is 1.5 ~ 3.0 times of theoretical value;
E, step A hot acid leached mud to be leached under acid chlorine salt system, after filtration villaumite leached mud and chloride leaching solution; Extract technology condition is: liquid-solid mass ratio is 7:1 ~ 11:1, and sodium chloride concentration is 200 ~ 300g/l, and calcium chloride concentration is 4 ~ 40g/l, and concentration of hydrochloric acid is 0.5 ~ 1.5mol/l, and temperature is 60 ~ 90 DEG C, and the time is 0.5 ~ 2.0 hour;
F, E step chloride leaching solution is carried out crystallisation by cooling, temperature is normal temperature, 6 ~ 12 hours time, after filtration lead chloride crystallization and crystalline mother solution, crystalline mother solution returns villaumite and leaches operation;
G, E step villaumite leached mud to be mixed with sodium hydroxide, carry out alkali fusion and obtain calcining; Alkali fusion processing condition are: temperature is 600 ~ 850 DEG C, and the time is 1 ~ 3 hour, and sodium hydroxide concentration is 0.6 ~ 1.2 times of villaumite leached mud quality;
H, the calcining water logging that G step alkali fusion obtains to be gone out, after filtration sodium stannate solution and water logging slag, water logging slag returns copper anode mud pretreatment process; Water logging processing condition are: liquid-solid mass ratio is 3:1 ~ 6:1, and temperature is 30 ~ 60 DEG C, and the time is 1 ~ 3 hour;
I, sodium stannate solution H step obtained carry out evaporative crystallization, and controlling sodium stannate solution proportion is 1.2 ~ 1.3, and obtain sodium stannate product, crystalline mother solution returns alkali fusion procedure.
Described all ingredients is technical grade reagent.
With the existing Measures compare reclaiming valuable metal from silver separating residue of copper anode slime, the present invention has following advantage: by barium high for content in point silver-colored slag, leached by hot acid and be separated with tin, lead, and then be separated with silver by nitric acid dissolve, the valuable metal such as tin, silver, lead by barium wraps up is released, thus achieving the high efficiente callback of the valuable metals such as tin, silver, lead, barium, plumbous, silver, tin and barium the rate of recovery reaches more than 97%, 92%, 90% and 95% respectively; Have technique simple, without " three wastes " discharge, metal recovery rate advantages of higher, be applicable to large-scale commercial production.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
As shown in drawings, the present invention can be widely used in comprehensively recovering valuable metal from all kinds of points of silver-colored slags, be particularly suitable for processing from the high silver separating residue of copper anode slime of the baric of copper-sulphide ores or copper scap production process output, its main component scope is (%) by weight percentage: Pb5.0 ~ 20.0, Ag1.0 ~ 10.0, Sn2.0 ~ 20.0, Ba10.0 ~ 40.0.
Embodiment 1:
Silver-colored slag main component is divided to be (%) by weight percentage: Pb16.0, Ag1.86, Sn7.5, Ba31.97.
Divide silver-colored slag to add vitriol oil 750ml toward 500g, leach 15 minutes at 350 DEG C, obtain hot acid leach liquor and hot acid leached mud.
The 150ml water dilution of hot acid leach liquor, obtains diluent and precipitation after filtration; Diluent returns copper anode mud pretreatment process, and precipitation 16mol/L nitric acid 350ml dissolves, and obtains barium sulfate precipitate and silver nitrate solution after filtration, barium sulfate precipitate dry weight 263.4g, containing the barium sulfate of 98.5%, and the barium rate of recovery 95.5%; The silver nitrate solution hydrazine hydrate reduction of theoretical value 3 times, obtain silver powder 8.63g, purity reaches 99.5%, silver raising recovery rate 92.3%.
Hot acid leached mud adds water 1400ml, sodium-chlor 475g, 6mol/L hydrochloric acid 170ml, calcium chloride 13.5g, stirs 2 hours, filter to obtain chloride leaching solution and villaumite leached mud at 60 DEG C; Chloride leaching solution normal temperature crystallisation by cooling 6 hours, filter to obtain lead chloride crystallization 106.6g, purity reaches 98%, and lead recovery is 97.3%, and crystalline mother solution returns villaumite and leaches operation; Villaumite leached mud adds sodium hydroxide 50g, after mixing at 700 DEG C alkali fusion 2 hours, the calcining obtained is placed and is cooled to room temperature, add water 300ml, stir 1.5 hours at 60 DEG C, filter to obtain sodium stannate solution and water logging slag, water logging slag returns copper anode mud pretreatment process; Sodium stannate solution is carried out evaporative crystallization, and controlling sodium stannate solution proportion is 1.2, and filtration, drying obtain sodium stannate product 81.45g, and purity reaches GB/T26040-2010 one-level, and the tin rate of recovery is 91.2%.
Embodiment 2:
Silver-colored slag main component is divided to be (%) by weight percentage: Pb11.5, Ag5.55, Sn8.5, Ba28.85.
Divide silver-colored slag to add vitriol oil 1000ml toward 500g, leach 25 minutes at 250 DEG C, obtain hot acid leach liquor and hot acid leached mud.
The 350ml water dilution of hot acid leach liquor, obtains diluent and precipitation after filtration; Diluent returns copper anode mud pretreatment process, and precipitation 16mol/L nitric acid 500ml dissolves, and obtains barium sulfate precipitate and silver nitrate solution after filtration, barium sulfate precipitate dry weight 240.5g, containing the barium sulfate of 98.9%, and the barium rate of recovery 97.0%; The silver nitrate solution hydrazine hydrate reduction of theoretical value 1.5 times, obtain silver powder 26.54g, purity reaches 99.1%, silver raising recovery rate 94.8%.
Add water 1200ml, sodium-chlor 450g, 6mol/L hydrochloric acid 150ml, calcium chloride 12.5g in hot acid leached mud, stir 1 hour at 80 DEG C, filter to obtain chloride leaching solution and villaumite leached mud; Chloride leaching solution normal temperature crystallisation by cooling 8 hours, filter to obtain lead chloride crystallization 76.2g, purity reaches 98.5%, and lead recovery is 97.3%, and crystalline mother solution returns villaumite and leaches operation.Villaumite leached mud adds sodium hydroxide 40g, after mixing at 600 DEG C alkali fusion 3 hours, the calcining obtained is placed and is cooled to room temperature, add water 280ml, stir 2.5 hours at 30 DEG C, filter to obtain sodium stannate solution and water logging slag, water logging slag returns copper anode mud pretreatment process; Sodium stannate solution is carried out evaporative crystallization, and the proportion controlling sodium stannate solution is 1.25, and filtration, drying obtain sodium stannate product 95.58g, and purity reaches GB/T26040-2010 one-level, and the tin rate of recovery is 94.5%.
Embodiment 3:
Silver-colored slag main component is divided to be (%) by weight percentage: Pb9.78, Ag7.13, Sn10.5, Ba24.95.
Divide silver-colored slag to add vitriol oil 900ml toward 500g, leach 10 minutes at 400 DEG C, obtain hot acid leach liquor and hot acid leached mud.
The 300ml water dilution of hot acid leach liquor, obtains diluent and precipitation after filtration; Diluent returns copper anode mud pretreatment process, and precipitation 16mol/L nitric acid 300ml dissolves, and obtains barium sulfate precipitate and silver nitrate solution after filtration, barium sulfate precipitate dry weight 210.9g, containing the barium sulfate of 98.7%, and the barium rate of recovery 98.2%; The silver nitrate solution hydrazine hydrate reduction of theoretical value 2 times, obtain silver powder 34.18g, purity reaches 99.2%, silver raising recovery rate 95.1%.
Hot acid leached mud adds water 1000ml, sodium-chlor 650g, 6mol/L hydrochloric acid 350ml, calcium chloride 45.5g, stirs 0.5 hour, filter to obtain chloride leaching solution and villaumite leached mud at 90 DEG C; Chloride leaching solution normal temperature crystallisation by cooling 12 hours, filter to obtain lead chloride crystallization 64.5g, purity reaches 98.9%, and lead recovery is 97.2%, and crystalline mother solution returns villaumite and leaches operation; Villaumite leached mud adds sodium hydroxide 60g, after mixing at 850 DEG C alkali fusion 1 hour, the calcining obtained is placed and is cooled to room temperature, add water 350ml, stir 2 hours at 40 DEG C, filter to obtain sodium stannate solution and water logging slag, water logging slag returns copper anode mud pretreatment process; Sodium stannate solution is carried out evaporative crystallization, and controlling sodium stannate solution proportion is 1.3, and filtration, drying obtain sodium stannate product 115.55g, and purity reaches GB/T26040-2010 one-level, and the tin rate of recovery is 92.4%.
Claims (1)
1. from a method for silver separating residue of copper anode slime comprehensively recovering valuable metal, it is characterized in that: comprise the following steps:
A, silver separating residue of copper anode slime is put into steel basin, adds the vitriol oil and carry out hot acid leaching, after filtration hot acid leached mud and hot acid leach liquor; Extract technology condition is: liquid-solid mass ratio is 2:1 ~ 10:1, and temperature is 200 ~ 500 DEG C, and the time is 5 ~ 60 minutes;
B, by step A hot acid leach liquor dilute with water, water consumption is 10% ~ 50% of hot acid leach liquor volume, after filtration diluent and precipitation, diluent returns copper anode mud pretreatment process;
C, the precipitation that step B water logging obtains is put into steel basin, add 16mol/L nitric acid dissolve, liquid-solid mass ratio is 1:1 ~ 3:1, after filtration barium sulfate precipitate and silver nitrate solution;
D, silver nitrate solution hydrazine hydrate step C obtained carry out reduction at normal temperatures and obtain silver powder, and hydrazine hydrate consumption is 1.5 ~ 3.0 times of theoretical value;
E, step A hot acid leached mud to be leached under acid chlorine salt system, after filtration villaumite leached mud and chloride leaching solution; Extract technology condition is: liquid-solid mass ratio is 7:1 ~ 11:1, and sodium chloride concentration is 200 ~ 300g/l, and calcium chloride concentration is 4 ~ 40g/l, and concentration of hydrochloric acid is 0.5 ~ 1.5mol/l, and temperature is 60 ~ 90 DEG C, and the time is 0.5 ~ 2.0 hour;
F, E step chloride leaching solution is carried out crystallisation by cooling, temperature is normal temperature, 6 ~ 12 hours time, after filtration lead chloride crystallization and crystalline mother solution, crystalline mother solution returns villaumite and leaches operation;
G, E step villaumite leached mud to be mixed with sodium hydroxide, carry out alkali fusion and obtain calcining; Alkali fusion processing condition are: temperature is 600 ~ 850 DEG C, and the time is 1 ~ 3 hour, and sodium hydroxide concentration is 0.6 ~ 1.2 times of villaumite leached mud quality;
H, the calcining water logging that G step alkali fusion obtains to be gone out, after filtration sodium stannate solution and water logging slag, water logging slag returns copper anode mud pretreatment process; Water logging processing condition are: liquid-solid mass ratio is 3:1 ~ 6:1, and temperature is 30 ~ 60 DEG C, and the time is 1 ~ 3 hour;
I, sodium stannate solution H step obtained carry out evaporative crystallization, and controlling sodium stannate solution proportion is 1.2 ~ 1.3, and obtain sodium stannate product, crystalline mother solution returns alkali fusion procedure.
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| 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 |
| CN106939377A (en) * | 2017-04-27 | 2017-07-11 | 中南大学 | A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled |
| CN107502744B (en) * | 2017-08-04 | 2019-02-01 | 江西铜业集团公司 | A kind of processing method of high lead barium silver separating residues |
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| CN108913912B (en) * | 2018-08-01 | 2020-11-13 | 济源职业技术学院 | Device for recovering copper from waste slag generated in copper smelting |
| CN113604672B (en) * | 2021-08-09 | 2022-10-04 | 四川省乐山锐丰冶金有限公司 | Method for recovering lead chloride and rare earth from lead-barium slag |
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| US4002544A (en) * | 1975-04-03 | 1977-01-11 | Outokumpu Oy | Hydrometallurgical process for the recovery of valuable components from the anode slime produced in the electrolytical refining of copper |
| 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 |
| CN101824546A (en) * | 2010-05-20 | 2010-09-08 | 北京科技大学 | Method for recovering silver from lead-separating liquid of silver-separating residue of copper anode slime |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002544A (en) * | 1975-04-03 | 1977-01-11 | Outokumpu Oy | Hydrometallurgical process for the recovery of valuable components from the anode slime produced in the electrolytical refining of copper |
| 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 |
| CN101824546A (en) * | 2010-05-20 | 2010-09-08 | 北京科技大学 | Method for recovering silver from lead-separating liquid of silver-separating residue of copper anode slime |
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