CN104611565A - A method of selectively recovering cobalt and copper from a cobalt-copper-zinc-manganese production waste solution - Google Patents
A method of selectively recovering cobalt and copper from a cobalt-copper-zinc-manganese production waste solution Download PDFInfo
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Abstract
The invention discloses a method of selectively recovering cobalt and copper from a cobalt-copper-zinc-manganese production waste solution. The cobalt and the copper are selectively recovered from the waste solution by adding manganese powder or manganese sheets into the waste solution and by adopting a one-time reduction or two-time reduction manner. The objective of selectively recovering the cobalt and the copper is achieved by controlling a process of the method, the size of the added manganese, the adding amount, the reaction temperature, the reaction time, and other factors. The recovery rate of the copper and the cobalt by the method is higher than 95%. The impurity content of recovered copper slag and cobalt slag is lower than 3%. The method is clean, efficient, simple in process, free of introduction of impurities, and beneficial to subsequent recovery of manganese, zinc, and other metals.
Description
Technical field
The present invention relates to chemical metallurgy and produce recovery and reuse of waste field, be specifically related to a kind of method of selective recovery cobalt copper from cobalt, nickel, copper hydrometallurgy waste material.
Background technology
In cobalt field of metallurgy, the main raw material producing cobalt metal is at present the heterogenite of outsourcing, can produce the metal product such as cobalt, copper with heterogenite as starting material.But the impurity such as outsourcing cobalt water ore deposit usual association copper MnZn calcium aluminium, in hydrometallurgy process, the flow process generally adopted in industry is: outsourcing cobalt raw material-sulfuric acid pulp dissolving-yellow modumite method deironing-P204 removal of impurities-P507 Extraction of Cobalt-backwash cobalt liquor-electrodeposited cobalt technical process, cobalt raw material extracts through P204, the impurity such as copper MnZn calcium aluminium enter organic phase, P204 load organic phases is again through persalt backwash, obtain the solution (removal of impurities liquid) being rich in copper cobalt MnZn calcium magnesium, generally speaking, this solution alkali precipitation is waste residue by manufacturing enterprise, takes out or stores up open circuit.Rough calculation, often produce the product of 1 ton of cobalt amount and from dedoping step, take away cobalt amount be greater than 20kg, also have the metals such as a large amount of copper, manganese, zinc through reasonably reclaiming, solid accumulation causes loss and the environmental pollution of valuable metal.In order to improve comprehensive utilization of resources level, researchist has carried out the technical study work of Call Provision, copper respectively in a large amount of from then on waste residue, such as use N235 solvent extraction zinc-copper cobalt, it is made to be separated with manganese calcium magnesium, N235 solvent extraction zinc-copper is easier to, but the percentage extraction of Extraction of Cobalt is lower, need medium to contain to be greater than the chlorion of 250g/L, therefore pre-concentration solution is needed, if add a large amount of hydrochloric acid, phase-splitting difficulty can be caused, load organic phases washing Call Provision copper, but the backwash of load organic zinc is quite difficult, and organic phase is difficult to recycle.Numerous and diverse, the industrial equipment investment of whole technical process is large, and the costs such as energy consumption are high, cannot drop into industrial application.Have document for the purpose of removal of impurities, the research method of beavy metal impurity in substitution method removing zinc solution or manganese solution, simply adds the metal more active than other heavy metals in this method.As by this process application at this, then the valuable metal such as cobalt copper still difficulty be recycled, impurity still cannot be opened a way.About the then little systematic research of active metal selectivity displacement heavy metal, data of literatures is less.Metal replacement method has that clean and effective, pollution-free, filtration velocity are fast, equipment and advantage simple to operate, and industrial application value potentiality is huge.But it is less in field of metallurgy research, does not form systematic method, also can follow without case history.
Summary of the invention
For prior art Problems existing, the present invention utilizes sheet and powdery manganese metal, and under the prerequisite not introducing impurity, produce selective recovery cobalt and copper waste liquid from cobalt copper zinc-manganese, technological operation is simple, clean and effective.
Above-mentioned purpose is realized by following proposal:
Produce a method for selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, said method comprising the steps of:
(1) joined by manganese powder in cobalt copper zinc-manganese waste liquid, temperature of reaction is 5 DEG C-85 DEG C, and the reaction times is 5min-60min; Wherein, in waste liquid, hydrionic concentration is 0.1-1mol/L, and when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and described waste liquid, the 1-1.5 of theoretical amount sum doubly;
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by;
(3) in the filtrate in step (2), add sheet manganese, temperature of reaction is 25 DEG C-85 DEG C, and the reaction times is 30min-180min; When the add-on of wherein said sheet manganese is cobalt ion complete reaction in manganese and described filtrate, the 1-20 of theoretical amount doubly;
(4) the solution filtration in step (3) is obtained cobalt slag and manganese slag, cobalt slag and manganese slag are returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycle.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, in the waste liquid of step (1), each metallic element ionic concn is respectively: mn ion 0.5-160g/L, zine ion 0.5-160g/L, cobalt ion 0.5-50g/L, cupric ion 0.5-50g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, described in step (1), the granularity of manganese powder is less than 50 orders.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, in the filtrate of step (2), each metallic element ionic concn is respectively: mn ion 0.5-200g/L, zine ion 0.5-160g/L, cobalt ion 0.5-30g/L, cupric ion 0.001-10g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, when the pH value of solution is 4 in step (3), solution is filtered and obtains cobalt slag and manganese slag.
Produce a method for selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, said method comprising the steps of:
(1) pH value of waste liquid is adjusted to 1-3;
(2) joined by manganese powder in cobalt copper zinc-manganese waste liquid, temperature of reaction is 5 DEG C-85 DEG C, reaction times 5min-70min; Wherein, when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and described waste liquid, the 1-1.5 of theoretical amount sum doubly;
(3) solution filters to obtain copper ashes and cobalt slag.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, in described waste liquid, each metallic element ionic concn is respectively: zine ion 0.5-160g/L, mn ion 0.5-200g/L, cobalt ion 0.5-30g/L, cupric ion 0.001-5g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, when the pH value of solution is 4 in step (2), solution is filtered to obtain copper ashes and cobalt slag.
According to the above-mentioned method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, the granularity of described manganese powder is less than 50 orders.
Beneficial effect of the present invention:
Method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese of the present invention, by the factor such as size, input amount, temperature of reaction, reaction times of the manganese metal of Controlling Technology flow process and input, propose the scheme of the chemical reaction rate slowing down reduction replacement(metathesis)reaction, solve various problems, add the too fast solution local pH that makes of granulated metal speed of reaction as disposable and raise too fast, a large amount of hydrolytic precipitation of MnZn aluminium, cause the problem such as colloidal precipitation filtration difficulty of recovery process poor selectivity, hydrolysis, reach the object of selective recovery cobalt, copper.Use method provided by the invention to reclaim copper cobalt metal, the rate of recovery of copper and cobalt is greater than 95%, and the foreign matter content of the copper cobalt slag of recovery is less than 3%.The method clean and effective, technique is simple, does not introduce impurity, is conducive to the recovery of the metals such as follow-up MnZn.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of an embodiment of the present invention.
Fig. 2 is the process flow sheet of another kind of embodiment of the present invention.
Embodiment
The present invention utilizes redox principle, produces the method for waste liquid selective recovery cobalt copper from cobalt copper MnZn.
The method of a kind of selective recovery cobalt copper from cobalt copper zinc-manganese production waste liquid of the present invention comprises the following steps:
(1) in cobalt copper zinc-manganese waste liquid, hydrionic concentration is 0.1-1mol/L, and each metallic element ionic concn is respectively: mn ion 0.5-160g/L, zine ion 0.5-160g/L, cobalt ion 0.5-50g/L, cupric ion 0.5-50g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.Granularity being less than 50 object manganese powders joins in waste liquid, and manganese powder and waste liquid react, and it is 5 DEG C-85 DEG C that temperature of reaction controls, and the reaction times is 5min-60min, and now the blueness of solution is taken off gradually.When the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid, the 1-1.5 of theoretical amount sum doubly.
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by.Now, in filtrate, each metallic element ionic concn is respectively: mn ion 0.5-200g/L, zine ion 0.5-160g/L, cobalt ion 0.5-30g/L, cupric ion 0.001-10g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
(3) in the filtrate in step (2), add sheet manganese, carry out secondary reduction, to ensure to reclaim the degree of depth, it is 25 DEG C-85 DEG C that temperature of reaction controls, and the reaction times is 30min-180min.When wherein the add-on of sheet manganese is cobalt ion complete reaction in manganese and filtrate, the 1-20 of theoretical amount doubly.
(4) filtered by solution, filtrate can be used for reclaiming zinc-manganese metal in follow-up flow process, and filter residue is cobalt slag and manganese slag, its air blast is dried up, and is milled to and is less than 50 order powderies, is then returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycles.Wherein, preferably, when in step (3), the pH of solution is 4, reaction terminating, now filters solution.
The mode that a kind of method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese of the present invention also can take a step to reduce, its step is specific as follows:
(1) in waste liquid, each metallic element ionic concn is respectively: zine ion 0.5-160g/L, mn ion 0.5-200g/L, cobalt ion 0.5-30g/L, cupric ion 0.001-5g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.The pH value of waste liquid is adjusted to 1-3.
(2) granularity being less than 50 object manganese powders joins in waste liquid, and temperature of reaction controls as being 5 DEG C-85 DEG C, reaction times 5min-70min.When the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid, the 1-1.5 of theoretical amount sum doubly.
(3) solution is filtered to obtain copper ashes and cobalt slag.After filter, solution can be used for reclaiming zinc-manganese metal.Wherein, preferably, when in step (2), the pH of solution is 4, reaction terminating, now filters solution.
Cobalt copper zinc-manganese waste liquid can be the abstraction impurity removal waste liquid from cobalt, metallurgy of nickel flow process, also can be other mineral such as pelagite ore deposit leach containing cobalt copper zinc-manganese solution.
Below in conjunction with specific embodiment, the present invention will be described.
Embodiment 1
(1) in cobalt copper zinc-manganese waste liquid, hydrionic concentration is 0.28mol/L, and each metallic element ionic concn is respectively: mn ion 80g/L, zine ion 7g/L, cobalt ion 17g/L, cupric ion 39g/L, calcium ion 12g/L, aluminum ion 0.5g/L.Granularity being less than 50 object manganese powders joins in waste liquid, and manganese powder and waste liquid react, and it is 80 DEG C that temperature of reaction controls, and the reaction times is 10min, and now the blueness of solution is taken off gradually.1 times of theoretical amount sum when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid.
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by.Now, cobalt ion 12g/L is contained in filtrate.
(3) in the filtrate in step (2), add sheet manganese, carry out secondary reduction, to ensure to reclaim the degree of depth, it is 80 DEG C that temperature of reaction controls, and the reaction times is 30min.2 times of theoretical amount when wherein the add-on of sheet manganese is cobalt ion complete reaction in manganese and filtrate.
(4) filtered by the solution in step (3), filtrate can be used for reclaiming zinc-manganese metal in follow-up flow process, and filter residue is cobalt slag and manganese slag, its air blast is dried up, and is milled to and is less than 50 order powderies, is then returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycles.
Embodiment 2
(1) in cobalt copper zinc-manganese waste liquid, hydrionic concentration is 0.78mol/L, and each metallic element ionic concn is respectively: mn ion 85g/L, zine ion 8g/L, cobalt ion 15.5g/L, cupric ion 36g/L, calcium ion 10g/L, aluminum ion 0.8g/L.Granularity being less than 50 object manganese powders joins in waste liquid, and manganese powder and waste liquid react, and it is 25 DEG C that temperature of reaction controls-, the reaction times is 30min, and now the blueness of solution is taken off gradually.1.5 times of theoretical amount sum when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid.
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by.Now, in filtrate, concentration of cobalt ions is 12g/L.
(3) in the filtrate in step (2), add sheet manganese, carry out secondary reduction, to ensure to reclaim the degree of depth, it is 70 DEG C that temperature of reaction controls, and the reaction times is 50min, and now the pH of solution is 4, reaction terminating.10 times of theoretical amount when wherein the add-on of sheet manganese is cobalt ion complete reaction in manganese and filtrate.
(4) filtered by the solution in step (3), filtrate can be used for reclaiming zinc-manganese metal in follow-up flow process, and filter residue is cobalt slag and manganese slag, its air blast is dried up, and is milled to and is less than 50 order powderies, is then returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycles.
Embodiment 3
(1) in cobalt copper zinc-manganese waste liquid, hydrionic concentration is 0.1mol/L, and each metallic element ionic concn is respectively: mn ion 0.5g/L, zine ion 0.5g/L, cobalt ion 1g/L, cupric ion 1g/L, calcium ion 0.5g/L, aluminum ion 0.5g/L.Granularity being less than 50 object manganese powders joins in waste liquid, and manganese powder and waste liquid react, and it is 5 DEG C that temperature of reaction controls, and the reaction times is 5min, and now the blueness of solution is taken off gradually.1 times of theoretical amount sum when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid.
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by.Now, in filtrate, each metallic element ionic concn is respectively: mn ion 1g/L, zine ion 0.5g/L, cobalt ion 0.5g/L, cupric ion 0.001g/L, calcium ion 0.5g/L, aluminum ion 0.5g/L.
(3) in the filtrate in step (2), add sheet manganese, carry out secondary reduction, to ensure to reclaim the degree of depth, it is 25 DEG C that temperature of reaction controls, and the reaction times is 30min.20 times of theoretical amount when wherein the add-on of sheet manganese is cobalt ion complete reaction in manganese and filtrate.
(4) filtered by solution, filtrate can be used for reclaiming zinc-manganese metal in follow-up flow process, and filter residue is cobalt slag and manganese slag, its air blast is dried up, and is milled to and is less than 50 order powderies, is then returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycles.
Embodiment 4
(1) in cobalt copper zinc-manganese waste liquid, hydrionic concentration is 1mol/L, and each metallic element ionic concn is respectively: mn ion 80g/L, zine ion 160g/L, cobalt ion 50g/L, cupric ion 50g/L, calcium ion 50g/L, aluminum ion 1g/L.Granularity being less than 50 object manganese powders joins in waste liquid, and manganese powder and waste liquid react, and it is 85 DEG C that temperature of reaction controls, and the reaction times is 60min, and now the blueness of solution is taken off gradually.1.5 times of theoretical amount sum when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid.
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by.Now, in filtrate, each metallic element ionic concn is respectively: mn ion 200g/L, zine ion 160g/L, cobalt ion 30g/L, cupric ion 10g/L, calcium ion 50g/L, aluminum ion 1g/L.
(3) in the filtrate in step (2), add sheet manganese, carry out secondary reduction, to ensure to reclaim the degree of depth, it is 85 DEG C that temperature of reaction controls, and the reaction times is 180min.10 times of theoretical amount when wherein the add-on of sheet manganese is cobalt ion complete reaction in manganese and filtrate.
(4) filtered by solution, filtrate can be used for reclaiming zinc-manganese metal in follow-up flow process, and filter residue is cobalt slag and manganese slag, its air blast is dried up, and is milled to and is less than 50 order powderies, is then returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycles.
Embodiment 5
(1) in waste liquid, each metallic element ionic concn is respectively: zine ion 0.5g/L, mn ion 0.5g/L, cobalt ion 0.5g/L, cupric ion 0.001g/L, calcium ion 0.5g/L, aluminum ion 0.5g/L.The pH value of waste liquid is adjusted to 1-3.
(2) granularity being less than 50 object manganese powders joins in waste liquid, and temperature of reaction controls as being 5 DEG C, reaction times 5min.1 times of theoretical amount sum when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid.
(3) solution in step (2) is filtered to obtain copper ashes and cobalt slag.After filter, solution can be used for reclaiming zinc-manganese metal.
Embodiment 6
(1) in waste liquid, each metallic element ionic concn is respectively: zine ion 160g/L, mn ion 200g/L, cobalt ion 30g/L, cupric ion 5g/L, calcium ion 50g/L, aluminum ion 1g/L.The pH value of waste liquid is adjusted to 1-3.
(2) granularity being less than 50 object manganese powders joins in waste liquid, and it is 85 DEG C that temperature of reaction controls, and reaction times 70min, now the pH of solution is 4.1.5 times of theoretical amount sum when now the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and waste liquid.
(3) solution in step (2) is filtered to obtain copper ashes and cobalt slag.After filter, solution can be used for reclaiming zinc-manganese metal.
Claims (9)
1. produce a method for selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, said method comprising the steps of:
(1) joined by manganese powder in cobalt copper zinc-manganese waste liquid, temperature of reaction is 5 DEG C-85 DEG C, and the reaction times is 5min-60min; Wherein, in waste liquid, hydrionic concentration is 0.1-1mol/L, and when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and described waste liquid, the 1-1.5 of theoretical amount sum doubly;
(2) solution is filtered to obtain copper ashes and cobalt slag, filtrate is stand-by;
(3) in the filtrate in step (2), add sheet manganese, temperature of reaction is 25 DEG C-85 DEG C, and the reaction times is 30min-180min; When the add-on of wherein said sheet manganese is cobalt ion complete reaction in manganese and described filtrate, the 1-20 of theoretical amount doubly;
(4) the solution filtration in step (3) is obtained cobalt slag and manganese slag, cobalt slag and manganese slag are returned in the cobalt copper zinc-manganese waste liquid in step (1) and recycle.
2. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 1, it is characterized in that, in the waste liquid of step (1), each metallic element ionic concn is respectively: mn ion 0.5-160g/L, zine ion 0.5-160g/L, cobalt ion 0.5-50g/L, cupric ion 0.5-50g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
3. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 1, it is characterized in that, described in step (1), the granularity of manganese powder is less than 50 orders.
4. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 1, it is characterized in that, in the filtrate of step (2), each metallic element ionic concn is respectively: mn ion 0.5-200g/L, zine ion 0.5-160g/L, cobalt ion 0.5-30g/L, cupric ion 0.001-10g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
5. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 1, is characterized in that, when the pH value of solution is 4 in step (3), is filtered by solution and obtains cobalt slag and manganese slag.
6. produce a method for selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese, it is characterized in that, said method comprising the steps of:
(1) pH value of waste liquid is adjusted to 1-3;
(2) joined by manganese powder in cobalt copper zinc-manganese waste liquid, temperature of reaction is 5 DEG C-85 DEG C, reaction times 5min-70min; Wherein, when the add-on of manganese powder is cobalt ion and cupric ion complete reaction in manganese and described waste liquid, the 1-1.5 of theoretical amount sum doubly;
(3) solution filters to obtain copper ashes and cobalt slag.
7. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 6, it is characterized in that, in described waste liquid, each metallic element ionic concn is respectively: zine ion 0.5-160g/L, mn ion 0.5-200g/L, cobalt ion 0.5-30g/L, cupric ion 0.001-5g/L, calcium ion 0.5-50g/L, aluminum ion 0.5-1g/L.
8. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 6, is characterized in that, when the pH value of solution is 4 in step (2), solution is filtered to obtain copper ashes and cobalt slag.
9. method of producing selective recovery cobalt copper waste liquid from cobalt copper zinc-manganese according to claim 6, it is characterized in that, the granularity of described manganese powder is less than 50 orders.
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| CN105274352A (en) * | 2015-09-30 | 2016-01-27 | 兰州金川新材料科技股份有限公司 | Method for separating copper, cobalt and manganese from mixture of copper, manganese, cobalt, calcium and zinc carbonate |
| CN105296754A (en) * | 2015-11-30 | 2016-02-03 | 北方工业大学 | Method for separating copper, cobalt and manganese from impurity-removed solution of copper, manganese, cobalt, calcium and zinc chloride |
| CN105648214A (en) * | 2016-01-18 | 2016-06-08 | 中南大学 | Method for vulcanizing and separating valuable metal in solution through controlled potential |
| CN105714116A (en) * | 2016-03-16 | 2016-06-29 | 中南大学 | Method for removing copper, cadmium, nickel and cobalt out of zinc sulfate solution through one step |
| CN105779787A (en) * | 2016-03-16 | 2016-07-20 | 中南大学 | Method for deep removing nickel and cobalt impurities in zinc hydrometallurgy solution |
| CN105861832A (en) * | 2016-06-17 | 2016-08-17 | 济源市华信科技有限公司 | Wet zinc smelting purifying and impurity removing method |
| CN105886763A (en) * | 2016-03-15 | 2016-08-24 | 中南大学 | Method for recovering cobalt from cobalt-containing solution |
| CN105967217A (en) * | 2016-05-06 | 2016-09-28 | 中南大学 | Method for recovery and utilization of all components in solution containing chlorides of copper and manganese |
| CN109609785A (en) * | 2018-12-20 | 2019-04-12 | 中国恩菲工程技术有限公司 | The method of cobalt is separated from cobalt, manganese carbonate mixture |
| CN110564961A (en) * | 2019-10-14 | 2019-12-13 | 湖南有色金属研究院 | Method for reducing leached hydrocobaltite |
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