CN104911354A - Method for separating Cu(II) and Me(II) from Cu(II)-Me(II)-Cl solution system - Google Patents
Method for separating Cu(II) and Me(II) from Cu(II)-Me(II)-Cl solution system Download PDFInfo
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- CN104911354A CN104911354A CN201510308504.4A CN201510308504A CN104911354A CN 104911354 A CN104911354 A CN 104911354A CN 201510308504 A CN201510308504 A CN 201510308504A CN 104911354 A CN104911354 A CN 104911354A
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Abstract
The invention discloses a method for separating Cu(II) and Me(II) from a Cu(II)-Me(II)-Cl solution system, wherein Me refers to one or more of Co, Ni, Mn and Zn. According to the precipitation character of Cu(II) in the Cu(II)-Me(II)-Cl solution system, by controlling the pH value of the solution and adopting a composite selective precipitant, the Cu(II) is preferentially precipitated from the Cu(II)-Me(II)-Cl solution system to realize effective separation of Cu(II) and Me(II).
Description
Technical field
The invention belongs to hydrometallurgy and resource and environment filed, be specifically related to the method for separation of C u (II) and Me (II) in a kind of Cu (II)-Me (II)-Cl (Me be in Co, Ni, Mn and Zn a kind and more than) solution system.
Background technology
In the wet underwater welding metallurgical process of non-ferrous metal cobalt, adopt cobaltous carbonate, cobaltous hydroxide and heterogenite to be the high-purity cobalt chloride product of raw material production, except containing except cobalt in raw material, go back the metals such as cupric, nickel, manganese, zinc.
After hydrometallurgical extraction cobalt chloride, the copper in raw material, nickel, manganese, zinc etc. and remaining cobalt are converted into corresponding chloride soln, form the solution system of Cu (II)-Me (II)-Cl.Prior art all adopts the full precipitation process Cu of sodium carbonate (II)-Me (II)-Cl solution system, and the mixed sediment of gained carbonate returns the process of pyrogenic process system, the copper that only recovery unit price is wherein higher and cobalt.This processing mode is except consuming a large amount of soda ash, more seriously pyrogenic attack carbonate mixed precipitation slag, the rate of recovery of cobalt and copper only has about 45%, cause a large amount of losses of cobalt and copper, and manganese and zinc are abandoned by slag making in pyrometallurgical smelting process, therefore pyrogenic attack Cu (II)-Me (II)-Cl solution system carbonate mixed precipitation slag technique is stopped using all.The annual carbonate mixed precipitation waste residue piled up is caused to reach thousands of tons of, wherein valuable metal cobalt about 80 tons (being worth 2,000 ten thousand yuan), copper 400 tons (being worth 2,000 ten thousand yuan), 1500 tons, manganese (being worth 1,300 ten thousand yuan) thus.How economical and efficient extract these valuable metals, become the difficult problem that cobalt smelting enterprise is urgently to be resolved hurrily.
Summary of the invention
The object of the invention is the novel method developing separation of C u (II) and Me (II) in a kind of Cu (II)-Me (II)-Cl solution system, estimating every year can from Cu (II)-Me (the II)-Cl solution extracted after cobalt, extract nearly 80 tons of cobalts, 400 tons of copper, more than 1000 ton manganese, significantly improve the rate of recovery of metal, improve the production technique of cobalt system, reduce the stacking place of a large amount of precipitation waste residue.
The object of the invention is to be achieved through the following technical solutions.
A kind of method of separation of C u (II) and Me (II) in Cu (II)-Me (II)-Cl solution system, first alkali lye is adopted to regulate Cu (II)-Me (II)-Cl solution system pH value 1.0 ~ 4.0, add composite parts precipitation agent selective precipitation Cu (II) again, realize effective separation of Cu (II) and Me (II) in Cu (II)-Me (II)-Cl solution system, Me be in Co, Ni, Mn and Zn a kind and more than; The composite parts precipitation agent of selective precipitation Cu (II) is the mixture of carbonate solution and bicarbonate solution.
Raw material of the present invention is after hydrometallurgical extraction cobalt chloride, copper during cobalt chloride leaching process is raw materials used, nickel, manganese, zinc and remaining cobalt are converted into corresponding chloride soln, Cu (II)-Me (the II)-Cl solution system of formation.
Cu (II)-Me (II)-Cl solution system pH value alkali lye used is regulated to be the mixing solutions of in ammoniacal liquor, sodium hydroxide, potassium hydroxide a kind or more in aforesaid method.The concentration of alkali lye is 2.5 ~ 10mol/L.
In aforesaid method, carbonate and supercarbonate are ammonium salt or sodium salt or sylvite.In composite parts precipitation agent, the ratio of the mole number of carbonate and supercarbonate is 5:1 ~ 10:1, both total volumetric molar concentrations are 1.0 ~ 5.0mol/L, according to each ionic concn and liquor capacity in Cu (II)-Me (II)-Cl solution, the consumption calculating compound precipitants is 200 ~ 1000ml.
In aforesaid method, selective precipitation Cu (II) temperature of reaction is 50 ~ 80 DEG C, the reaction times is 2 ~ 5h.
The advantage of invention and positively effect
By selective precipitation Cu (II) in Cu (II)-Me (II)-Cl solution system, smelt effective separation of extracting valuable metal in gained Cu (II)-Me (II)-Cl solution system for cobalt and recovery provides basis.
Embodiment
Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1: the mixing solutions getting 1000ml cupric chloride and Manganous chloride tetrahydrate, 60 DEG C are warmed up under mechanical stirring, drip the ammoniacal liquor of 350ml3.0mol/L, after the pH value of solution is adjusted to 3.5, add the mixing solutions (mol ratio of sodium carbonate and sodium bicarbonate is 5:1) of sodium carbonate that 350ml total concn is 2.5mol/L and sodium bicarbonate, continue reaction 3h, vacuum filtration, measure the concentration of copper and manganese in filtrate, calculate the deposition rate of each metal for (%): copper 98.5, manganese 2.5.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, sodium carbonate and sodium bicarbonate compound, can realize effectively being separated of copper and manganese.
Embodiment 2: the mixing solutions getting 1500ml cupric chloride and cobalt chloride, 80 DEG C are warming up under mechanical stirring, drip the ammoniacal liquor of 800ml2.5mol/L and the mixed alkali liquor (mol ratio of ammonia and potassium hydroxide is 4:1) of potassium hydroxide, after the pH value of solution is adjusted to 2.0, add the mixing solutions (mol ratio of sodium carbonate and bicarbonate of ammonia is 3:2) of sodium carbonate that 450ml total concn is 3.5mol/L and bicarbonate of ammonia, continue reaction 5h, vacuum filtration, measure the concentration of copper and cobalt in filtrate, calculate the deposition rate of each metal for (%): copper 99.3, cobalt 1.2.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, sodium carbonate and bicarbonate of ammonia compound, can realize effectively being separated of copper and cobalt.
Embodiment 3: the mixing solutions getting 800ml cupric chloride and nickelous chloride, 70 DEG C are warmed up under mechanical stirring, drip sodium hydroxide and the potassium hydroxide mixed alkali liquor (mol ratio of sodium hydroxide and potassium hydroxide is 5:1) of 200ml3.5mol/L, after the pH value of solution is adjusted to 2.5, add the mixing solutions (mol ratio of salt of wormwood and sodium bicarbonate is 5:3) of salt of wormwood that 245ml total concn is 3.0mol/L and sodium bicarbonate, continue reaction 4h, vacuum filtration, measure the concentration of copper and mickel in filtrate, calculate the deposition rate of each metal for (%): copper 98.7, nickel 3.5.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, salt of wormwood and sodium bicarbonate compound, can realize effectively being separated of copper and nickel.
Embodiment 4: the mixing solutions getting 2000ml cupric chloride and zinc chloride, 50 DEG C are warmed up under mechanical stirring, drip the ammoniacal liquor of 900ml3.5mol/L, the mixed alkali liquor (ammonia: sodium hydroxide: potassium hydroxide mol ratio is 5:3:1) of sodium hydroxide and potassium hydroxide, after the pH value of solution is adjusted to 3.0, add the mixing solutions (mol ratio of sodium carbonate and sodium bicarbonate is 5:4) of sodium carbonate that 650ml total concn is 3.0mol/L and sodium bicarbonate, continue reaction 2h, vacuum filtration, measure copper and zinc concentration in filtrate, calculate the deposition rate of each metal for (%): copper 97.6, zinc 0.5.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, sodium carbonate and sodium bicarbonate compound, can realize effectively being separated of copper and zinc.
Embodiment 5: the mixing solutions getting 1000ml cupric chloride, cobalt chloride and Manganous chloride tetrahydrate, 60 DEG C are warmed up under mechanical stirring, drip the sodium hydroxide lye of 380ml 3.5mol/L, after the pH value of solution is adjusted to 2.3, add the mixing solutions (mol ratio of sodium carbonate and sodium bicarbonate is 6:1) of sodium carbonate that 400ml total concn is 2.5mol/L and sodium bicarbonate, continue reaction 3h, vacuum filtration, measure the concentration of copper, cobalt and manganese in filtrate, calculate the deposition rate of each metal for (%): copper 96.8, cobalt 1.7 and manganese 1.5.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, sodium carbonate and sodium bicarbonate compound, can realize copper and cobalt, being effectively separated of manganese.
Embodiment 6: get 800ml cupric chloride, cobalt chloride, the mixing solutions of nickelous chloride and Manganous chloride tetrahydrate, 60 DEG C are warmed up under mechanical stirring, drip ammoniacal liquor and the sodium hydroxide mixed alkali liquor (mol ratio of ammonia and sodium hydroxide is 6:1) of 195ml3.5mol/L, after the pH value of solution is adjusted to 2.4, add the mixing solutions (mol ratio of sodium carbonate and sodium bicarbonate is 6:1) of sodium carbonate that 280ml total concn is 2.5mol/L and sodium bicarbonate, continue reaction 3h, vacuum filtration, measure copper in filtrate, cobalt, the concentration of nickel and manganese, calculate the deposition rate of each metal for (%): copper 95.1, cobalt 2.3, nickel 0.9 and manganese 3.5.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, sodium carbonate and sodium bicarbonate compound, can realize copper and cobalt, nickel, being effectively separated of manganese.
Embodiment 7: get 600ml cupric chloride, cobalt chloride, nickelous chloride, the mixing solutions of Manganous chloride tetrahydrate and zinc chloride, 60 DEG C are warmed up under mechanical stirring, drip ammoniacal liquor and the potassium hydroxide mixed alkali liquor (mol ratio of ammonia and potassium hydroxide is 6:1) of 150ml 3.5mol/L, after the pH value of solution is adjusted to 2.5, add the mixing solutions (mol ratio of sodium carbonate and sodium bicarbonate is 6:1) of sodium carbonate that 210ml total concn is 2.5mol/L and sodium bicarbonate, continue reaction 3h, vacuum filtration, measure copper in filtrate, cobalt, nickel, manganese and zinc concentration, calculate the deposition rate of each metal for (%): copper 96.2, cobalt 0.8, nickel 1.2, manganese 2.3, zinc 1.7.Test-results shows, sinks the conditions such as the proportioning of α-benzoinoxime, concentration and consumption by controlling the pH value of reaction system, sodium carbonate and sodium bicarbonate compound, can realize copper and cobalt, nickel, manganese, being effectively separated of zinc.
Claims (7)
1. the method for separation of C u (II) and Me (II) in Cu (II)-Me (II)-Cl solution system, it is characterized in that, first alkali lye is adopted to regulate Cu (II)-Me (II)-Cl solution system pH value 1.0 ~ 4.0, add composite parts precipitation agent selective precipitation Cu (II) again, realize effective separation of Cu (II) and Me (II) in Cu (II)-Me (II)-Cl solution system, Me be in Co, Ni, Mn and Zn a kind and more than; The composite parts precipitation agent of selective precipitation Cu (II) is the mixture of carbonate solution and bicarbonate solution.
2. the method for separation of C u (II) and Me (II) in Cu according to claim 1 (II)-Me (II)-Cl solution system, it is characterized in that, after hydrometallurgical extraction cobalt chloride, copper in raw material, nickel, manganese, zinc and remaining cobalt are converted into corresponding chloride soln, form the solution system of Cu (II)-Me (II)-Cl.
3. the method for separation of C u (II) and Me (II) in Cu according to claim 1 (II)-Me (II)-Cl solution system, it is characterized in that, regulate Cu (II)-Me (II)-Cl solution system pH value alkali lye used to be ammoniacal liquor, sodium hydroxide, the mixing solutions of a kind of potassium hydroxide or more.
4. in Cu (II)-Me (the II)-Cl solution system according to claim 1 or 2 or 3, the method for separation of C u (II) and Me (II), is characterized in that, the total concn of alkali lye is 2.5 ~ 10mol/L.
5. the method for separation of C u (II) and Me (II) in Cu according to claim 1 (II)-Me (II)-Cl solution system, is characterized in that, carbonate and supercarbonate are ammonium salt or sodium salt or sylvite.
6. the method for separation of C u (II) and Me (II) in Cu (II)-Me (the II)-Cl solution system according to claim 1 or 2 or 5, it is characterized in that, in composite parts precipitation agent, the ratio of the mole number of carbonate and supercarbonate is 5:1 ~ 10:1, both total volumetric molar concentrations are 1.0 ~ 5.0mol/L, according to each ionic concn and liquor capacity in Cu (II)-Me (II)-Cl solution, the consumption calculating compound precipitants is 200 ~ 1000ml.
7. the method for separation of C u (II) and Me (II) in Cu according to claim 6 (II)-Me (II)-Cl solution system, it is characterized in that, selective precipitation Cu (II) temperature of reaction is 50 ~ 80 DEG C, the reaction times is 2 ~ 5h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105861830A (en) * | 2016-06-01 | 2016-08-17 | 金川集团股份有限公司 | Method for preparing large-granule copper-rich dross by selectively precipitating Cu in Cu(II)-Me(II)-Cl solution system |
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| CN102888513A (en) * | 2012-10-15 | 2013-01-23 | 甘肃民族师范学院 | Method of fully separating copper, manganese, zinc, cobalt and calcium chloride solution |
| CN102887545A (en) * | 2012-10-15 | 2013-01-23 | 兰州大学 | Method for preparing electronic-grade manganese carbonate from manganese-copper-zinc-cobalt-calcium chloride solution |
| CN104212970A (en) * | 2014-09-19 | 2014-12-17 | 北京大学 | Method for enrichment and recovery of valuable metals Ni, Cu and Co from tailing sand in Cu-Ni mine |
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Patent Citations (3)
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| CN102888513A (en) * | 2012-10-15 | 2013-01-23 | 甘肃民族师范学院 | Method of fully separating copper, manganese, zinc, cobalt and calcium chloride solution |
| CN102887545A (en) * | 2012-10-15 | 2013-01-23 | 兰州大学 | Method for preparing electronic-grade manganese carbonate from manganese-copper-zinc-cobalt-calcium chloride solution |
| CN104212970A (en) * | 2014-09-19 | 2014-12-17 | 北京大学 | Method for enrichment and recovery of valuable metals Ni, Cu and Co from tailing sand in Cu-Ni mine |
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| CN105861830A (en) * | 2016-06-01 | 2016-08-17 | 金川集团股份有限公司 | Method for preparing large-granule copper-rich dross by selectively precipitating Cu in Cu(II)-Me(II)-Cl solution system |
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Application publication date: 20150916 |