CN104131316A - Electrolysis method for separating copper from cobalt and nickel in chloride ion ammoniacal system and application of products thereof - Google Patents
Electrolysis method for separating copper from cobalt and nickel in chloride ion ammoniacal system and application of products thereof Download PDFInfo
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Abstract
The invention discloses a method for separating copper from cobalt and nickel in a chloride ion ammoniacal system. The method mainly adopts an electrolysis separation technology, which comprises the following steps: dissolving a proper amount of at least one of copper salt, cobalt salt and nickel salt in a leached liquid of an analogue mineral sample containing copper, cobalt and nickel, adding ammonium chloride and a proper amount of active metal chloride into the solution, finally adding concentrated ammonia water so as to obtain an electrolytic system; carrying out electrolysis on the electrolytic system by taking graphite as the positive electrode and a stainless steel plate as the negative electrode, controlling the voltage to carry out electrolysis separation, and carrying out deposition to obtain the copper powder with high copper content and low nickel and cobalt content and electrolysis residual liquid with enriched nickel and cobalt. The electrolysis method has the advantages of simple and efficient steps, low cost, environmental friendliness, and good resource comprehensive utilization rate.
Description
Technical field
The present invention relates to a kind of method of Separation and Recovery and comprehensive utilization copper cobalt nickel, relate in particular in the copper cobalt nickel mixed solution of a kind of ammonia gonosome system the directly material metallurgical method of separating copper, cobalt nickel.
Background technology
Copper, cobalt, nickel etc. are very important non-ferrous metals, the special strategic materials of development for hi-tech industry, be widely used in the key areas that aerospace, defence and military, electronic information, new forms of energy etc. involve the interests of the state and the people, in the development construction of national economy, occupy critical role.In earth mineral, copper, cobalt, nickel are mainly with its sulfide, oxide compound symbiotic co-existence.Along with the decline day by day of Mineral resources grade, traditional acid technological process can not meet the needs of processing copper, cobalt (nickel), people's ammonia process extract technology that begins one's study gradually.
Leach in cupric oxide cobalt nickel minerals process at ammonia process, Cu, Co, Ni and ammonia form title complex [Me (NH
3)
i]
2+enter solution, and Mn, Zn, Ca, Fe, Si etc. hardly with NH
3reaction, thus reach the object that selectivity leaches.Ammonia leaches the problems such as acidic leaching long flow path, cleaner and acid & alkali liquid input amount are large that solved; The recycling of ammonia and ammonium salt also can reduce production costs greatly.
In the leach liquor that ammonia leaching copper cobalt nickel minerals obtains, main component is the ammonia title complex of copper cobalt nickel, and subsequent technique mainly comprises separation and the utilization of copper, cobalt, nickel.The method of separating copper and cobalt nickel mainly contains following four kinds at present: (1) substitution method, and abroad some large-scale nickel refining factory owners will use nickel powder substitution method, and economical not, cost is high; (2) solvent extration, multi-stage solvent extraction could be deepened copper removal, and it is difficult to carry out large industrialized application; (3) ion exchange method, the method leaching requirement is large, is difficult to process; (4) chemical precipitation method, it mainly uses hydrolysis or sulfuration method precipitated copper, but easily causes the loss of nickel cobalt.
Therefore study the economic, practical technology in the solution system of cupric cobalt nickel, valuable element being separated, this is significant for leach from now on extraction valuable metal from copper cobalt nickel minerals.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, a kind of method of electrolytic separation copper, cobalt nickel in chlorion ammonia gonosome system that provides that step is simple efficient, cost is low, environmentally friendly, comprehensive utilization of resources is good, and the application of the product that the method obtains is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes be a kind of in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, described method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, at least one in a certain amount of mantoquita, cobalt salt, nickel salt dissolved, in lysate, add ammonium chloride and a certain amount of active metal muriate again, finally add strong aqua preparation to obtain electrolyte system; Due in chlorion ammonia gonosome system, copper cobalt nickel metal ion main and amino molecule and chlorion complexing, electrolytic conductivity is lower, add a certain amount of active metal muriate under the prerequisite that electrolysis is not produced detrimental impurity, to improve electrical conductivity of solution, be conducive to the raising of Faradaic current efficiency;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, by controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the chlorion ammonia electrolysis of nickel cobalt enrichment; Kept dry after copper powder adopts deionized water repetitive scrubbing, suds immersion, absolute ethanol washing to process.
In above-mentioned method, preferred, described mantoquita is cupric chloride, and in described electrolyte system, the concentration control of cupric ion is 0.25M～0.75M.
In above-mentioned method, preferred, described cobalt salt is cobalt chloride, and in described electrolyte system, the concentration control of cobalt ion is 0.025M～0.075M.
In above-mentioned method, preferred, described nickel salt is nickelous chloride, and in described electrolyte system, the concentration control of nickel ion is 0.0125M～0.0375M.
In above-mentioned method, preferably, described mantoquita is cupric chloride, described cobalt salt is cobalt chloride, described nickel salt is nickelous chloride, in described electrolyte system, the concentration control of cupric ion is 0.25M～0.75M, and in described electrolyte system, the concentration control of cobalt ion is 0.025M～0.075M, and in described electrolyte system, the concentration control of nickel ion is 0.0125M～0.0375M.
In above-mentioned method, preferred, the concentration of the ammonium chloride adding in described electrolyte system is 1M～5M, and the mol ratio of ammonium ion and ammonium radical ion is (1～2): 1.Control ammonia ammonium ratio, this is mainly because NH
3～NH
4 +a kind of damping fluid, proportioning difference, GOLD FROM PLATING SOLUTION belongs to the complexing degree varies sample of ion, and the pH value of electrolytic solution also can be different, and then can affect electrolytic reaction and carry out, and promote electrolytic reaction to carry out to the direction of more expectation by preferred control ammonia ammonium than being conducive to.
In above-mentioned method, preferred, described active metal muriate is Repone K and/or sodium-chlor, and the muriatic concentration control in described active metal is 0.5M～1.5M.
In above-mentioned method, preferred, in described electrolytic separation process, the useful area of electrolysis cathode is 10～20cm
2, electrolysis temperature control is 30 DEG C～50 DEG C, cathode potential control is-0.6V～-1.0V that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.
In technique scheme of the present invention, our research conclusion shows that main electrolytic reaction is the title complex [Cu (NH that copper and ammonia generate
3)
i]
2+, obtaining negative electrode copper powder by electrolysis, anode generates nitrogen; In chlorion ammonia gonosome system, copper cobalt nickel and ammonia are through progressively complexing, between title complex, there is complex equilibrium, therefore copper ion concentration, foreign metal cobalt nickel ion concentration and ammonia ammonium are than the balance that all can affect reaction, and then affect copper cobalt nickel Stability constants at different levels and decomposition voltage, thereby electrolysis is produced to considerable influence.The present invention, by various raw materials, material and ionic concn in optimal control reaction raw materials system, make reaction of the present invention smooth, and quality product is better; Consider that the amino molecule in copper cobalt nickel ion and solution can form complex compound, the specific conductivity in electrolytic solution can be lower, by adding muriate can improve electrical conductivity of solution.
As a total technical conceive, the present invention also provides the application of the product that a kind of aforesaid method obtains, the copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.Preferred, the massfraction of described copper powder more than 99.56%, and in copper powder the massfraction of cobalt and nickel all below 0.25%.
Compared with prior art, the invention has the advantages that:
1. the present invention uses electrolytic process separating copper and cobalt nickel, the product copper powder obtaining can be used as the raw material of Alpaka, and the nickel cobalt enrichment mixed solution obtaining after electrolysis can be used as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material, resource is fully utilized and maximizing the benefits.
2. traditional copper and cobalt nickel separation method, as solvent extraction or ion-exchange, need to pass through multistep technique, and can produce environmentally harmful wastewater and waste materials.And chemical replacement method or precipitator method technical process are long, reagent consumption is many, and cost is high.Comparatively speaking, the present invention uses electrolytic process separating copper and cobalt nickel, has directly obtained copper powder and nickel cobalt mixed solution, has greatly shortened operational path, has saved technique consuming time, and whole processing step is simple, process efficiency is high, environmental friendliness, good product consistency.
In sum, preparation technology of the present invention not only step is simple, efficient, and cost is low, environmentally friendly, and comprehensive utilization of resources is good, application prospect is very wide from now on.
Embodiment
For the ease of understanding the present invention, below in connection with preferred embodiment, the present invention is done more comprehensively, described meticulously, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, all technical terms of hereinafter using are identical with the implication that those skilled in the art understand conventionally.Technical term used herein, just in order to describe the object of specific embodiment, is not to be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material used in the present invention, reagent, instrument and equipment etc. all can be bought and be obtained or can prepare by existing method by market.
Embodiment 1:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 21.31g cupric chloride, 2.95g cobalt chloride and 1.49g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 18.52g ammonium chloride and 29.22g in leach liquor, finally add 9.13ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-0.6V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 2:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 21.31g cupric chloride, 5.90g cobalt chloride and 2.98g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 18.52g ammonium chloride and 29.22g in leach liquor, finally add 18.26ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-0.8V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 3:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 21.31g cupric chloride, 8.85g cobalt chloride and 4.47g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 37.04g ammonium chloride and 29.22g in leach liquor, finally add 18.26ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-1.0V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 4:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 42.62g cupric chloride, 5.90g cobalt chloride and 2.98g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 18.52g ammonium chloride and 29.22g in leach liquor, finally add 18.26ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-0.6V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 5:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 42.62g cupric chloride, 8.85g cobalt chloride and 4.47g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 18.52g ammonium chloride and 29.22g in leach liquor, finally add 9.13ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-0.8V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 6:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 42.62g cupric chloride, 2.95g cobalt chloride and 1.49g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 37.04g ammonium chloride and 29.22g in leach liquor, finally add 9.13ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-1.0V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 7:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 63.92g cupric chloride, 8.85g cobalt chloride and 4.46g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 37.04g ammonium chloride and 29.22g in leach liquor, finally add 9.13ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-0.6V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 8:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 63.92g cupric chloride, 2.95g cobalt chloride and 1.49g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 37.04g ammonium chloride and 29.22g in leach liquor, finally add 18.26ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-0.8V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Embodiment 9:
Of the present invention in chlorion ammonia gonosome system the method for electrolytic separation copper, cobalt nickel, the method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, add respectively 63.92g cupric chloride, 5.90g cobalt chloride and 2.98g nickelous chloride, again to the sodium-chlor mixed dissolution that adds 18.52g ammonium chloride and 29.22g in leach liquor, finally add 9.13ml strong aqua, preparation obtains the electrolyte system of 500ml;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, positive plate with distilled water flushing repeatedly, abrasive paper for metallograph sanding and polishing step by step for negative plate, uses with distilled water flushing is clean after the oil removing of use dilute alkaline soln more afterwards; By controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, in electrolytic separation process, the useful area of electrolysis cathode is 10cm
2, electrolysis temperature control is 40 DEG C, cathode potential control is-1.0V (VS.SCE) that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.Deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.The copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
Above-described embodiment gained copper powder is dissolved with concentrated nitric acid, after deionized water dilution, detect through ICP, in copper powder, the composition of copper cobalt nickel is as shown in table 1 below.
The experiment condition of table 1: embodiment 1～9 and test result
As seen from the above table, the present invention uses the method for electrolytic process separating copper, cobalt nickel in chlorion ammonia gonosome system, there is good effect, in the copper powder obtaining, the content of copper can reach more than 99.56%, the loss of nickel cobalt is little, and after electrolysis in the nickel cobalt pregnant solution of gained copper ion concentration also lower than 0.01M, can be directly used in the preparation of nickel-cobalt-manganese ternary material.In sum, than traditional copper and mickel cobalt separation method, the present invention has obvious advantage, has good application prospect.
Claims (10)
1. a method for electrolytic separation copper, cobalt nickel in chlorion ammonia gonosome system, described method mainly adopts electrolytic separation method, comprises the following steps:
(1) preparation electrolyte system: in the simulation sample ore leach liquor of cupric, cobalt, nickel, at least one in a certain amount of mantoquita, cobalt salt, nickel salt dissolved, in lysate, add ammonium chloride and a certain amount of active metal muriate again, finally add strong aqua preparation to obtain electrolyte system;
(2) electrolytic separation: in the electrolyte system of above-mentioned preparation, taking graphite as electrolytic anode, taking stainless steel plate as electrolysis cathode, by controlling voltage electrolytic process, above-mentioned electrolyte system is carried out to electrolytic separation, deposition obtains the high and copper powder that nickel cobalt contents is low of copper content, and the remaining liquid of the electrolysis of nickel cobalt enrichment.
2. method according to claim 1, is characterized in that: described mantoquita is cupric chloride, and in described electrolyte system, the concentration control of cupric ion is 0.25M～0.75M.
3. method according to claim 1, is characterized in that: described cobalt salt is cobalt chloride, and in described electrolyte system, the concentration control of cobalt ion is 0.025M～0.075M.
4. method according to claim 1, is characterized in that: described nickel salt is nickelous chloride, and in described electrolyte system, the concentration control of nickel ion is 0.0125M～0.0375M.
5. method according to claim 1, it is characterized in that: described mantoquita is cupric chloride, described cobalt salt is cobalt chloride, described nickel salt is nickelous chloride, in described electrolyte system, the concentration control of cupric ion is 0.25M～0.75M, in described electrolyte system, the concentration control of cobalt ion is 0.025M～0.075M, and in described electrolyte system, the concentration control of nickel ion is 0.0125M～0.0375M.
6. according to the method described in any one in claim 1～5, it is characterized in that: the concentration of the ammonium chloride adding in described electrolyte system is 1M～5M, the mol ratio of ammonium ion and ammonium radical ion is (1～2): 1.
7. according to the method described in any one in claim 1～5, it is characterized in that: described active metal muriate is Repone K and/or sodium-chlor, the muriatic concentration control in described active metal is 0.5M～1.5M.
8. according to the method described in any one in claim 1～5, it is characterized in that: in described electrolytic separation process, the useful area of electrolysis cathode is 10～20cm
2, electrolysis temperature control is 30 DEG C～50 DEG C, cathode potential control is-0.6V～-1.0V that the terminal control copper ion concentration of electrolytic separation is lower than 0.01M.
9. the application of the product that method obtains as described in any one in claim 1～8, it is characterized in that: the copper content copper powder high and that nickel cobalt contents is low that deposition is obtained is applied as the raw material of Alpaka, and the remaining liquid of the electrolysis of nickel cobalt enrichment is applied as the raw material of preparing lithium cell nickel-cobalt-manganese ternary positive electrode material.
10. application according to claim 9, is characterized in that: the massfraction of described copper powder more than 99.56%, and in copper powder the massfraction of cobalt and nickel all below 0.25%.
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| CN104701524A (en) * | 2015-03-03 | 2015-06-10 | 中南大学 | Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte |
| CN104831065A (en) * | 2015-04-09 | 2015-08-12 | 长沙矿冶研究院有限责任公司 | Method for separating nickel and cobalt from manganese in high manganese-cobalt ratio nickel-cobalt-manganese raw material |
| CN108034822A (en) * | 2017-12-06 | 2018-05-15 | 贵州红星电子材料有限公司 | A kind of method for removing copper ion in tri compound sulfate liquor |
| CN112921356A (en) * | 2021-01-22 | 2021-06-08 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
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| CN104701524A (en) * | 2015-03-03 | 2015-06-10 | 中南大学 | Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte |
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| CN108034822A (en) * | 2017-12-06 | 2018-05-15 | 贵州红星电子材料有限公司 | A kind of method for removing copper ion in tri compound sulfate liquor |
| CN108034822B (en) * | 2017-12-06 | 2019-11-19 | 贵州红星电子材料有限公司 | A method of copper ion in removal tri compound sulfate liquor |
| CN112921356A (en) * | 2021-01-22 | 2021-06-08 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
| CN112921356B (en) * | 2021-01-22 | 2022-05-27 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
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