CN103966457A - Method for recovering valuable metals from copper anode casting washery slag - Google Patents
Method for recovering valuable metals from copper anode casting washery slag Download PDFInfo
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- CN103966457A CN103966457A CN201410221758.8A CN201410221758A CN103966457A CN 103966457 A CN103966457 A CN 103966457A CN 201410221758 A CN201410221758 A CN 201410221758A CN 103966457 A CN103966457 A CN 103966457A
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- Prior art keywords
- copper
- washery slag
- copper anode
- barium
- anode casting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to a copper anode casting washery slag reutilization technique, particularly a method for recovering valuable metals from copper anode casting washery slag. The method comprises the following steps: drying and dehydrating copper anode casting washery slag, carrying out hot acid leaching under the action of an oxidizer to simultaneously leach barium and copper in the washery slag into the solution, cooling the leaching solution to normal temperature, diluting with water, and filtering to obtain a barium sulfate precipitate and a copper sulfate solution, wherein the precipitate can directly return to the copper anode casting procedure as a releasing agent, and the copper sulfate solution is used for recovering copper. The hot acid leaching is utilized to leach the high-content barium sulfate in the washery slag so as to effectively release barium-coated copper, thereby efficiently recovering the barium and copper from the washery slag, wherein the recovery rates of the barium and copper are respectively higher than 99%. The method has the advantages of short technical process, simple equipment, high metal recovery rate and the like, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to copper anode casting washery slag reutilization technology, particularly a kind of method that reclaims valuable metal from copper anode casting washery slag.
Background technology
Copper anode casting cycle, separates with mold for ease of anode copper, often need on mold, spray high temperature resistant releasing agent.At present, copper anode casting releasing agent mainly contains barium sulfate, bone meal, Graphite Powder 99, china clay in powder 4 clocks, wherein barium sulfate because of hydrophobicity good, be sprayed on the mould of certain temperature, moisture content can comparatively fast evaporate, and the pore producing on positive plate relatively less, is widely used at each copper smelting plant.In copper anode casting cycle, it is cooling that the copper anode plate that casting obtains enters cooling pool, sometimes also rinse with water blast gun, now, cover the releasing agent on positive plate surface and part copper or already oxidised Red copper oxide and can come off and enter pond, these materials have formed copper anode casting washery slag jointly.
Copper anode casting washery slag contains a large amount of copper, Red copper oxide and barium sulfate.Current, most smelteries by copper anode cast washery slag return to smelting furnace or send slag select workshop reclaim copper.But because releasing agent granularity is very thin, in copper anode casting cooling basin, settling velocity is slower, often covers copper or Red copper oxide surface; In removal process, because barium sulfate chemical property is comparatively stable, be under general condition difficult to be dissolved in acid or alkali equal solvent, make a large amount of wrapped copper or Red copper oxide along with barium sulfate directly enters slag or selects slag, the rate of recovery of copper is low, and barium sulfate releasing agent fails to obtain recycle.
Summary of the invention
The object of this invention is to provide a kind of method that reclaims valuable metal from copper anode casting washery slag, solve the problem that copper recovery is low, barium cannot recycle.
For achieving the above object, the technical scheme that the present invention takes: a kind of method that reclaims valuable metal from copper anode casting washery slag, comprises the following steps:
First the washery slag of copper anode being cast is dry, puts into stirred leaching tank and carries out hot acid leaching, under the effect of hydrogen peroxide or atmospheric oxygen agent, the barium in washery slag and copper is leached into liquid simultaneously; Hot acid leaching condition is: sulfuric acid concentration is 18mol/L, and liquid-solid mass ratio is 2:1～10:1, and temperature is 200～500 DEG C, and the time is 5～60 minutes, hydrogen peroxide consumption is theoretical amount 3～5 times, or air intake is theoretical amount 6～10 times;
Hot acid leaches the principal reaction occurring:
BaSO
4+H
2SO
4＝Ba(HSO
4)
2，
Cu
2O+H
2SO
4＝CuSO
4+Cu+H
2O，
2Cu+2H
2SO
4+O
2＝2CuSO
4+2H
2O，
Cu+H
2SO
4+H
2O
2＝CuSO
4+2H
2O；
Then hot acid leach liquor is cooled to normal temperature, with the water dilution of hot acid leach liquor volume 10%～50%, filters to obtain barium sulfate precipitate and copper-bath; Barium sulfate precipitate directly returns to copper anode casting operation as releasing agent, and copper-bath reclaims copper with electrolysis or crystallization mode; The reaction occurring when dilution is:
Ba(HSO
4)
2＝BaSO
4↓+H
2SO
4。
It is below 1% that copper anode casting washery slag is dried to moisture mass ratio.
The all ingredients such as described sulfuric acid, hydrogen peroxide are technical grade reagent.
The present invention adopts hot acid leaching method, barium and copper are leached into liquid simultaneously, again by dilution, be separable barium and copper, the barium that recovery obtains can directly be reused as releasing agent, and copper reclaims with copper sulfate form, can adopt common method (electrolysis or crystallization) to reclaim copper, copper and the barium rate of recovery, all up to more than 99%, have been saved resource; Have that technical process is short, equipment is simple, metal recovery rate advantages of higher, is applicable to large-scale commercial production.
Brief description of the drawings
Accompanying drawing is process flow sheet of the present invention.
Embodiment
As shown in drawings, the present invention can be widely used in reclaiming barium and copper from copper anode casting washery slag, and its main component scope is (%) by weight percentage: Cu10.0～50.0, Ba10.0～50.0.In embodiment, the moisture mass ratio of copper anode casting washery slag is below 1%.
Embodiment 1:
Copper anode casting washery slag main component is (%): Cu24.9, Ba40.5, H by weight percentage
2o0.9.
Add vitriol oil 2.0L toward the dry copper anode of 500g casting washery slag, constantly adding mass percent by 2.0L/ per hour (t washery slag) speed is 30% hydrogen peroxide, leaches 50 minutes at 250 DEG C; Hot acid leach liquor is cooled to after normal temperature, with the dilution of 0.5L water, obtains after filtration copper-bath 2.6L and barium sulfate precipitate 345g, diluent cupric 47.5g/L, precipitation barium sulfate-containing 99.0%, the rate of recovery of copper and barium reaches respectively 99.1% and 99.2%.
Embodiment 2:
Copper anode casting washery slag main component is (%): Cu44.1, Ba25.5, H by weight percentage
2o0.8.
Add vitriol oil 2.5L toward the dry copper anode of 500g casting washery slag, constantly adding mass percent by 9.5L/ per hour (t washery slag) speed is 30% hydrogen peroxide, leaches 20 minutes at 350 DEG C; Hot acid leach liquor is cooled to after normal temperature, with the dilution of 1.0L water, obtains after filtration copper-bath 3.8L and barium sulfate precipitate 218g, diluent cupric 57.5g/L, precipitation barium sulfate-containing 99.2%, the rate of recovery of copper and barium reaches respectively 99.1% and 99.8%.
Embodiment 3:
Copper anode casting washery slag main component is (%): Cu23.5, Ba42.4, H by weight percentage
2o0.9.
The copper anode casting washery slag dry toward 500g adds vitriol oil 2.0L, constantly passes into air by per minute 3.0L/ (t washery slag) speed, leaches 60 minutes at 200 DEG C; Hot acid leach liquor is cooled to after normal temperature, with the dilution of 0.5L water, obtains after filtration copper-bath 2.7L and barium sulfate precipitate 365g, diluent cupric 43.3g/L, precipitation barium sulfate-containing 98.0g/L, the rate of recovery of copper and barium reaches respectively 99.5% and 99.3%.
Embodiment 4:
Copper anode casting washery slag main component is (%): Cu43.4, Ba29.7, H by weight percentage
2o0.8.
The copper anode casting washery slag dry toward 500g adds vitriol oil 2.5L, constantly passes into air by per minute 34.5L/ (t washery slag) speed, leaches 10 minutes at 450 DEG C; Hot acid leach liquor is cooled to after normal temperature, with the dilution of 1.0L water, obtains after filtration copper-bath 3.8L and barium sulfate precipitate 255g, diluent cupric 56.8g/L, precipitation barium sulfate-containing 98.5g/L, the rate of recovery of copper and barium reaches respectively 99.5% and 99.5%.
Claims (4)
1. one kind is reclaimed the method for valuable metal from copper anode casting washery slag, it is characterized in that: comprise the following steps: by dry the copper anode washery slag of casting, under the effect of hydrogen peroxide or atmospheric oxygen agent, carry out hot acid leaching, barium in washery slag and copper are leached into liquid simultaneously, be cooled to afterwards normal temperature, dilute with water, filters to obtain barium sulfate precipitate and copper-bath.
2. a kind of method that reclaims valuable metal from copper anode casting washery slag according to claim 1, it is characterized in that: the washery slag of first copper anode being cast is dry, put into stirred leaching tank and carry out hot acid leaching, under the effect of hydrogen peroxide or atmospheric oxygen agent, the barium in washery slag and copper are leached into liquid simultaneously; Hot acid leaching condition is: sulfuric acid concentration is 18mol/L, and liquid-solid mass ratio is 2:1～10:1, and temperature is 200～500 DEG C, and the time is 5～60 minutes, hydrogen peroxide consumption is theoretical amount 3～5 times, or air intake is theoretical amount 6～10 times;
Hot acid leaches the principal reaction occurring:
BaSO
4+H
2SO
4＝Ba(HSO
4)
2，
Cu
2O+H
2SO
4＝CuSO
4+Cu+H
2O，
2Cu+2H
2SO
4+O
2＝2CuSO
4+2H
2O，
Cu+H
2SO
4+H
2O
2＝CuSO
4+2H
2O；
Then hot acid leach liquor is cooled to normal temperature, with the water dilution of hot acid leach liquor volume 10%～50%, filters to obtain barium sulfate precipitate and copper-bath; Barium sulfate precipitate directly returns to copper anode casting operation as releasing agent, and copper-bath reclaims copper with electrolysis or crystallization mode; The reaction occurring when dilution is:
Ba(HSO
4)
2＝BaSO
4↓+H
2SO
4。
3. according to a kind of method that reclaims valuable metal from copper anode casting washery slag described in claim 1 or 2, it is characterized in that: it is below 1% that copper anode casting washery slag is dried to moisture mass ratio.
4. according to a kind of method that reclaims valuable metal from copper anode casting washery slag described in claim 1 or 2, it is characterized in that: Best Applying Condition: be that copper anode below 1% casting washery slag adds vitriol oil 2.0L by the moisture mass ratio of 500g, the speed of per minute 3.0L/t washery slag constantly passes into air, leaches 60 minutes at 200 DEG C; Hot acid leach liquor is cooled to after normal temperature, with the dilution of 0.5L water, obtains after filtration copper-bath and barium sulfate precipitate.
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|---|---|---|---|
| CN201410221758.8A CN103966457B (en) | 2014-05-23 | 2014-05-23 | A kind of method reclaiming valuable metal from copper anode casting washery slag |
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| CN201410221758.8A CN103966457B (en) | 2014-05-23 | 2014-05-23 | A kind of method reclaiming valuable metal from copper anode casting washery slag |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329931A (en) * | 2015-11-20 | 2016-02-17 | 金川集团股份有限公司 | Method for treating barium-containing waste residues in nickel chloride production process |
| CN106244814A (en) * | 2016-08-31 | 2016-12-21 | 紫金铜业有限公司 | A kind of method that Copper Anode Plate Casting process barium sulfate releasing agent recycles |
| CN112626340A (en) * | 2020-12-07 | 2021-04-09 | 阳谷祥光铜业有限公司 | Treatment method of copper anode plate washing slag |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB161655A (en) * | 1920-01-09 | 1921-04-11 | Philip Alexander Mackay | An improved method of obtaining strontium and barium sulphates from their native sulphates |
| ZA744920B (en) * | 1974-08-01 | 1976-03-31 | African Explosives & Chem | Improvements in the treatment of barytes |
| SU1763371A1 (en) * | 1990-09-26 | 1992-09-23 | Производственное Объединение "Южполиметалл" | Method of barium sulfate extraction from natural barite |
| CN102936657A (en) * | 2011-08-15 | 2013-02-20 | 江西格林美资源循环有限公司 | Method for metal recovery by ceramic capacitor |
-
2014
- 2014-05-23 CN CN201410221758.8A patent/CN103966457B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB161655A (en) * | 1920-01-09 | 1921-04-11 | Philip Alexander Mackay | An improved method of obtaining strontium and barium sulphates from their native sulphates |
| ZA744920B (en) * | 1974-08-01 | 1976-03-31 | African Explosives & Chem | Improvements in the treatment of barytes |
| SU1763371A1 (en) * | 1990-09-26 | 1992-09-23 | Производственное Объединение "Южполиметалл" | Method of barium sulfate extraction from natural barite |
| CN102936657A (en) * | 2011-08-15 | 2013-02-20 | 江西格林美资源循环有限公司 | Method for metal recovery by ceramic capacitor |
Non-Patent Citations (2)
| Title |
|---|
| 王晓辉等: "溶析结晶法制备高纯度亚微米硫酸钡粒子", 《无机材料学报》, vol. 20, no. 04, 20 July 2005 (2005-07-20) * |
| 赖建林等: "铜冶炼阳极炉浇铸渣制取饲料级硫酸铜", 《无机盐工业》, vol. 31, no. 06, 20 December 1999 (1999-12-20) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329931A (en) * | 2015-11-20 | 2016-02-17 | 金川集团股份有限公司 | Method for treating barium-containing waste residues in nickel chloride production process |
| CN106244814A (en) * | 2016-08-31 | 2016-12-21 | 紫金铜业有限公司 | A kind of method that Copper Anode Plate Casting process barium sulfate releasing agent recycles |
| CN106244814B (en) * | 2016-08-31 | 2018-06-22 | 紫金铜业有限公司 | A kind of method that Copper Anode Plate Casting process barium sulfate releasing agent recycles |
| CN112626340A (en) * | 2020-12-07 | 2021-04-09 | 阳谷祥光铜业有限公司 | Treatment method of copper anode plate washing slag |
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| CN103966457B (en) | 2016-01-20 |
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Effective date of registration: 20210519 Address after: Room 501-506, Zhongchuang space, No.1 torch Avenue, Ganzhou hi tech Industrial Development Zone, Ganxian District, Ganzhou City, Jiangxi Province, 341000 Patentee after: Jiangxi Shanning Technology Co.,Ltd. Address before: 341000 No. 86 Hongqi Avenue, Jiangxi, Ganzhou Patentee before: Jiangxi University of Science and Technology |
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