CN107815540A - A kind of method of hydrometallurgy metal nickel cobalt and its salt product - Google Patents

A kind of method of hydrometallurgy metal nickel cobalt and its salt product Download PDF

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CN107815540A
CN107815540A CN201711329940.5A CN201711329940A CN107815540A CN 107815540 A CN107815540 A CN 107815540A CN 201711329940 A CN201711329940 A CN 201711329940A CN 107815540 A CN107815540 A CN 107815540A
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solution
cobalt
electrodeposition
nickel
metal
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栗秀臣
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/06—Refining
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt

Abstract

The invention discloses a kind of hydrometallurgy metal nickel cobalt and its method for salt product, this method is obtaining the crude metal block of main grade nickel or cobalt content >=80% in a kind of electrodeposition from sulphuric leachate of offer, diaphragm electrolysis is carried out as anode using this metal derby again or electrolysis with ion-exchange film refines, obtain high purity nickel, the method of cobalt product, present invention process principle is simple, cost is low, it is green, the process of technology maturation, the process does not produce pernicious gas, processing procedure technical conditions are stablized easily-controllable, it is that efficient method can be reached with low cost in actual applications.

Description

A kind of method of hydrometallurgy metal nickel cobalt and its salt product
Technical field
The present invention relates to smelting process field, in particular to the side of a kind of hydrometallurgy metal nickel cobalt and its salt product Method.
Background technology
At present, the cobalt element product such as cobalt metal or cobalt powder, cobaltosic oxide, various cobalt raw materials institute in wet smelting process The processing step of progress mainly includes sulfuric acid leaching dissolving, iron removaling, abstraction impurity removal, extracting and enriching, the removal of impurities of ion exchange concentration, chlorine Change system electrodeposition produces metallic cobalt or makes other cobalt salts, and this mode of production production procedure is long, cost is high, especially chlorination body It is that a large amount of waste chlorines of output need to carry out absorption processing with alkali during electrodeposition produces metallic cobalt, cost is high, pollution environment, because This, designs that a kind of technological principle is simple, cost is low, green, technology maturation process is various equivalent modifications Urgent problem.
The content of the invention
In order to solve the above technical problems, technical scheme provided by the invention is：A kind of hydrometallurgy metal nickel cobalt and its salt The method of class product, comprises the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Sulfuric acid leaching is carried out to nickel cobalt raw material and forms leaching system, gained leaches Liquid is the sulfuric acid mixed salt solution containing different kinds of ions such as cobalt, copper, nickel, iron, zinc, lead, manganese, chromium.
(2) electrodeposition is carried out by raw material of sulphuric leachate：Carried out by raw material of the sulfuric acid mixed salt solution that step (1) obtains Electrodeposition forms electrodeposition system, and electrodeposition anode uses the insoluble anode under sulfuric acid system, and electrodeposition negative electrode is using titanium net, titanium plate or stainless The conductive metallic materials such as steel plate, under the conditions of electrodeposition, the element based on the metal ions such as the higher copper of electrode potential, nickel, cobalt Separate out to form metallic monolith negative electrode in negative electrode, anode reaction releases oxygen and produces H+。
(3) solution circulates：In step (2) electrolytic deposition process, solution acidity rise, the higher solution of electrodeposition system acidity with The solution of raw material sulphuric acid leaching system is circulating system, and solution goes step (1) leaching system supplement master again when electrodeposition acidity raises Grade concentration of metal ions, acidity reduces and goes step (2) electrodeposition system again after leaching.
(4) impurity is separated：For step (3) solution in electrodeposition and leaching cyclic process, the electrode potential such as manganese, zinc, iron is low Impurity composition concentration constantly raises, and as impurity total concentration >=20g/L, liquid is stand-by after periodically extracting the electrodeposition of certain volume out, and New leachate is supplemented, keeps foreign ion total concentration≤80g/L in solution recycle system, makes electrodeposition and leaches cyclic process not shape Product is separated out based on main grade cobalt into crystallization, negative electrode.
(5) liquid after the electrodeposition that step (4) is extracted out, after reclaiming electrodeposition using chemical precipitation method, ion-exchange or extraction The valuable metals such as copper, nickel, cobalt in liquid, reclaim the valuable metal come and be again introduced into production system from process is leached, it is impure Waste water removes Waste Water Treatment.
(6) metallic nickel, cobalt are produced：The cathode block using metal nickel cobalt as main grade that step (2) obtains, is put into after scrubbed Make anode in refining chlorination system electrolytic cell, using diaphragm electrolysis or electrolysis with ion-exchange film technique productions high pure metal nickel cobalt and its salt Class product.
(7) in step (2) electrolytic deposition process, the higher metal ion of electrode potential preferentially separates out in solution, by controlling electricity The tank voltage of product process, make the precipitation voltage of the tank voltage impurity element low less than electrode potential, this foreign ion is not in negative electrode Upper electrodeposition separates out, and reaches the purpose of isolation of purified purification.
(8) in step (2) electrolytic deposition process, the higher metal ion of electrode potential preferentially separates out in solution, by controlling electricity Product process cathode-current density≤380A/m2, solution temperature >=45 DEG C, solution flow through linear velocity >=0.1m/s of cathode surface, The higher metal ion of electrode potential is supplemented and preferentially separated out in time in cathode surface, when main grade concentration of metal ions >= During 5g/L, impurity content≤10% of precipitation, as main grade concentration of metal ions≤5g/L, the impurity element of precipitation contains Amount≤20%.
(9) step (6) refining process Anodic liquid is laggard through the mode deep purifying such as extraction or chemical precipitation, ion exchange Enter to cathodic region and supplement main grade concentration of metal ions.
Further, main grade nickel or concentration of cobalt ions >=5g/L in the middle gained leachate of the step (1), leachate PH value is controlled 0~4.0.
Further, the pH value of circulating system solution is controlled 0~4.0 in the step (2).
Further, cobalt grade >=80% of step (4) negative electrode output object.
Further, step (1) leaching system can be that sulfuric acid leaching, ammonia leach, or Cyanide Leaching is different Leaching Systems subsequent processes principle it is identical.
Further, also obtained between the step (1) and step (2) including the use of extraction, displacement method separating step (1) The high ion of the electrode potentials such as the copper of the sulphuric leachate arrived, avoid separating out in electrolytic deposition process formed galvanic cell influence main grade into The precipitation of part.
Further, in step (2) electrolytic deposition process, boric acid or Boratex are incorporated in solution.
Further, in step (2) electrolytic deposition process, using electrolytic cell constant voltage electrodeposition method, electrodeposition tank voltage is controlled, Enable electrodeposition voltage main grade element is separated out in negative electrode, with the reduction of main grade concentration of metal ions in solution, keep Tank voltage is constant, and DC current reduces, and the more negative impurity element of coordination electrode potential does not separate out largely, the amount of precipitation of foreign ion Account for total amount of precipitation≤10%, as main grade concentration≤5g/L, the impurity element amount of precipitation account for total amount of precipitation≤20%.
Further, the step (2) is in sulfuric acid, nitric acid, hydrochloric acid, ammonia or complex or a variety of systems mixing situation In lower carry out electrolytic deposition process, anode electrochemical reaction can release oxygen, can also be answered according to solution compolision situation precipitated phase Oxidation product.
The purpose of the present invention is aiming at nickel cobalt class raw material smelting process difficulty is high, heavy-polluted problem, there is provided Yi Zhongcong Electrodeposition obtains the crude metal block of main grade nickel or cobalt content >=80% in sulphuric leachate, then using this metal derby as anode carry out every Film is electrolysed or electrolysis with ion-exchange film refining, obtains high purity nickel, the method for cobalt product, present invention process principle is simple, cost is low, green Environmental protection, the process of technology maturation, the process does not produce pernicious gas, processing procedure technical conditions are stablized easily-controllable, is Efficient method can be reached with low cost in actual applications.
(1) it is using nickel or cobalt as the metal derby of main grade, master that intermediate products are obtained in step (2) sulfuric acid system electrolytic deposition process Grade >=80%, this metal derby can the electrochemical dissolution liquid making under the conditions of peracid, can obtain main grade nickel or cobalt content it is high, The low solution of impurity content, nickel salt, cobalt salt class product are done after purification.
(2) in step (2) sulfuric acid system electrolytic deposition process solution system controlling pH, acidity is lower, electrolytic deposition process electric current Efficiency is higher, impurity precipitation percentage is higher, and acidity is higher, and it is lower that electrolytic deposition process current efficiency is lower, impurity separates out percentage.
(3) the crude metal block of the present invention main grade nickel or cobalt content >=80% that electrodeposition obtains from sulphuric leachate, then Diaphragm electrolysis or electrolysis with ion-exchange film refining are carried out by anode of this metal derby, obtains high purity nickel, cobalt product, this process is same Standard electrode EMF suitable for element is negative value, main grade element and the larger element of impurity element standard electrode EMF difference Hydrometallurgy.
Embodiment
Embodiment one
A kind of method of hydrometallurgy metal nickel cobalt and its salt product, comprises the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Black nickel cobalt slag is selected as nickel cobalt raw material, this raw material is subjected to pulp, Sulfuric acid leaching is carried out, chlorion generation chlorine is discharged and handled by absorption during sulfuric acid leaching, using sulfur dioxide as reducing agent Nickelic cobalt ions in reducing solution, the sulphuric leachate that pH is 1~2 is obtained, contains Co in solution2+：27g/L、Ni2+： 45g/L、Fe2+：4.5g/L、Mn2+：3.2g/L、Cu2+：The impurity such as 2.5g/L.
(2) removal of impurity is gone：Black nickel cobalt slag is added into the leachate obtained by step (1), using the nickel in black nickel cobalt slag with Cobalt reaction in solution, nickel are dissolved into solution, and cobalt becomes Co (OH)3Sedimentation, controls the dosage of black nickel cobalt slag, makes to contain in solution Nickeliferous in cobalt≤0.02g/L, black cobalt slag≤2%.
(3) the black cobalt slag for obtaining step (2) carries out reduction of dissolved using sulfuric acid and sulfur dioxide, obtain containing cobalt concentration >= 60g/L, nickel concentration≤4g/L solution, simultaneously containing corresponding copper, manganese, iron tramp ion.
(4) solution obtained step (3) carries out iron replacement copper removal, then reuses nickel extractant and removes nickel, make copper from Sub- concentration is down to≤and 0.0001g/L, nickel concentration be down to≤0.001g/L.
(5) electrowinning with insoluble anode is carried out after the solution that step (4) obtains being made into boronic acid containing sodium 3g/L solution, with titanium plate Negative electrode is done, obtains thick cobalt metal derby, thick cobalt block is containing cobalt >=96%, cupric >=2.5%, iron≤0.01%；Use sodium hydroxide solution The pH of electrolytic deposition process solution is adjusted 1~4, continuous electrodeposition to concentration of cobalt ions≤5g/L.
(6) the thick cobalt block obtained using step (5) is put into chlorination system diaphragm cell as anode after scrubbed, production 99.98% high pure metal cobalt, electrolytic process Anodic liquid is after abstraction impurity removal and ion exchange depth purification as catholyte Continuous supplementation is into production process.
(7) the low cobalt solution that step (5) obtains returns step (1) and recycled, when sour in the low cobalt solution that step (5) obtains During radical ion >=190g/L, the valuable metal in solution is reclaimed after carbonate precipitation cobalt, then through ion exchange depth, has been handled Becoming waste liquid after finishing send waste water station to handle.
(8) the high nickel solution that step (2) obtains, by this solution in the way of step (5) the thick nickel cathode block of output, thick nickel Block is nickeliferous >=97%, cupric≤0.5%, iron≤0.01%；With the pH of sodium hydroxide solution adjustment solution 1~4, continuous electrodeposition To nickel ion concentration≤5g/L.
(9) the thick nickel block that step (8) obtains is raw material, is produced in the way of step (6) in nickel electrowinning system 99.98% high purity nickel product；The low nickel solution that step (8) obtains is handled in the way of step (7).
Embodiment two
A kind of method of hydrometallurgy metal nickel cobalt and its salt product, comprises the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Black nickel cobalt slag, outsourcing cobalt salt class are selected as nickel cobalt raw material, by outsourcing Cobalt salt class raw material uses sulfuric acid leaching after carrying out pulp, obtains the sulphuric leachate that pH is 1~2.5, contains Co in solution2+：31g/ L、Ni2+：0.5g/L、Fe2+：7.5g/L、Mn2+：7.7g/L、Cu2+：The metal ions such as 4.3g/L.
(2) copper removal：Step (1) resulting solution is subjected to copper removal, LIX extractants extract copper removal, and solution cupric drops after copper removal To 0.3g/L.
(3) black nickel cobalt slag is added in the solution obtained to step (2), it is anti-using the cobalt in the nickel and solution in black nickel cobalt slag Should, nickel is dissolved into solution, and the cobalt in solution becomes Co (OH)3Sedimentation, the dosage of black nickel cobalt slag is controlled, make in solution containing cobalt≤ 0.01g/L, nickel ion concentration reaches 32.5g/L in solution；The cobalt slag that settles out is nickeliferous >=5% when, continue and cobalt-bearing leaching solution Reaction, make cobalt-bearing leaching solution excessive, the nickel in cobalt slag is all changed into bivalent nickel ion dissolving in the solution, and obtained cobalt slag is nickeliferous ≤ 0.2%.
(4) the cobalt slag for obtaining step (3) carries out reduction of dissolved using sulfuric acid and sodium sulfite, obtain containing cobalt concentration >= 60g/L, nickel concentration≤0.5g/L solution, simultaneously containing foreign ions such as corresponding copper, manganese, iron, chromium.
(5) solution obtained using nickel extractant processing step (4), makes nickel concentration be down to≤0.001g/L.
(6) solution obtained step (5) carries out electrowinning with insoluble anode, and negative electrode is done with titanium plate, and cathode-current density 300~ 350A/m2, thick cobalt metal derby is obtained, thick cobalt block is containing total impurities≤0.2% such as cobalt >=98%, cupric >=0.5%, iron and manganese； The pH for adjusting solution in continuous electrolytic deposition process with sodium hydroxide solution is maintained at 0.5~3, and continuous electrodeposition to concentration of cobalt ions≤ 5g/L。
(7) the thick cobalt block obtained using step (6) is put into chlorination system diaphragm cell, produced as anode after scrubbed 99.98% high pure metal cobalt, electrolytic process Anodic liquid is after abstraction impurity removal and ion exchange depth purification as catholyte Continuous supplementation is into production process.
(8) the low cobalt solution that step (6) obtains returns step (1) and recycled, when sour in the low cobalt solution that step (6) obtains During radical ion >=200g/L, after carbonate precipitation cobalt, then after ion exchange depth reclaims valuable metal, waste liquid send waste water station Processing.
(9) the high nickel solution that step (3) obtains, by this solution in the way of step (6) the thick nickel cathode block of output, thick nickel Block is nickeliferous >=96%, cupric≤1.5%, total amount≤0.3% such as ferrimanganic；In production process solution is adjusted with sodium hydroxide solution PH is 0.5~3, and using the continuous electrodeposition of control flume voltage method, because voltage is constant when nickel ion concentration is low, current density is decreased to 200~30A/m2, nickel ion concentration is decrease continuously to≤2g/L in the solution containing nickel ion.
(10) the thick nickel block that step (9) obtains is raw material, is produced in the way of step (7) in nickel electrowinning system 99.98% high purity nickel product；The low nickel solution that step (9) obtains is handled in the way of step (8).
Continuously run with above steps, stably produce qualified products.
Embodiment three
A kind of method of hydrometallurgy metal nickel cobalt and its salt product, comprises the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Outsourcing nickel salt class raw material is selected as nickel cobalt raw material, by outsourcing nickel salt class Raw material uses sulfuric acid leaching after carrying out pulp, obtains the sulphuric leachate that pH is 1~2.5, contains Ni in solution2+：45g/L、Co2+： 3.2g/L、Fe2+：3.7g/L、Mn2+：2.6g/L、Cu2+：The metal ions such as 2.9g/L.
(2) step (1) resulting solution is subjected to copper removal, LIX extractants extract copper removal, and solution cupric is down to after copper removal 0.2g/L。
(3) oxidation of black nickel cobalt slag or sodium chlorate is added in the solution obtained to step (2) and removes cobalt, the cobalt in solution is with Co (OH)3Sedimentation, makes to contain cobalt≤0.01g/L in solution, nickel ion concentration reaches 43.5g/L in solution, and filtering solution obtains solid-state Black cobalt slag.
(4) the high nickel solution for obtaining step (2), electrowinning with insoluble anode is carried out, negative electrode, cathode-current density are done with titanium plate 320~350A/m2, obtain thick nickel metal derby, thick nickel block is nickeliferous >=97%, cupric≤0.6%, the total impurities such as iron and manganese≤ 0.2%；The pH for adjusting solution in continuous electrolytic deposition process with sodium hydroxide solution is maintained at 0.5~3, is connected using control flume voltage method Continuous electrodeposition, to nickel ion concentration≤2g/L.
(5) the thick nickel block obtained using step (4) is put into chlorination system diaphragm cell, produced as anode after scrubbed 99.98% high-purity metal nickel, electrolytic process Anodic liquid is after abstraction impurity removal and ion exchange depth purification as catholyte Continuous supplementation is into production process.
(6) the low nickel solution that step (4) obtains returns step (1) and recycled, when sour in the low nickel solution that step (4) obtains During radical ion >=200g/L, after sodium carbonate coprecipitated nickel hydroxide, then after ion exchange depth reclaims valuable metal, waste liquid send waste water station Processing.
(7) the black cobalt slag of solid-state that step (3) obtains, production cobalt product is focused on when running up to a certain amount of.
Continuously run with above steps, stably produce qualified products.
Example IV
A kind of method of hydrometallurgy metal nickel cobalt and its salt product, comprises the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Outsourcing nickel salt class raw material is selected as nickel cobalt raw material, by outsourcing nickel salt class Raw material uses sulfuric acid leaching after carrying out pulp, obtains the sulphuric leachate that pH is 1~2.5, contains Ni in solution2+：45g/L、Co2+： 1.2g/L、Fe2+：3.7g/L、Mn2+：2.6g/L、Cu2+：The metal ions such as 2.9g/L.
(2) step (1) resulting solution is subjected to copper removal, LIX extractants extract copper removal, and solution cupric is down to after copper removal 0.2g/L。
(3) oxidation of black nickel cobalt slag or sodium chlorate is added in the solution obtained to step (2) and removes cobalt, the cobalt in solution is with Co (OH)3Sedimentation, makes to contain cobalt≤0.01g/L in solution, nickel ion concentration reaches 43.5g/L in solution, and filtering solution obtains solid-state Black cobalt slag.
(4) the high nickel solution for obtaining step (2), electrowinning with insoluble anode is carried out, negative electrode, cathode-current density are done with titanium plate 300~350A/m2, obtains thick nickel metal derby, thick nickel block is nickeliferous >=97%, cupric≤1%, the total impurities such as iron and manganese≤ 0.5%.
(5) in the continuous electrolytic deposition process of step (4), solution is in step (1) leaching process and the continuous electrolytic deposition process of step (4) Circulation, solution pH after step (4) electrodeposition are down to 0.5~1, return to step (1) and leached, leachate removes through step (2) again After copper, make nickel-copper ratio >=10 in solution, now solution returns to step (4) continuous electrodeposition again.
(6) as acid ion >=200g/L in the low nickel solution that step (4) obtains, after sodium carbonate coprecipitated nickel hydroxide, then pass through After ion exchange depth recovery valuable metal, waste liquid send waste water station to handle.
(7) the thick nickel metal derby that step (4) obtains does anode, and chlorination system diaphragm cell is put into after scrubbed, production Go out 99.98% high-purity metal nickel, electrolytic process Anodic liquid is after abstraction impurity removal and ion exchange depth purification as negative electrode Liquid continuous supplementation is into production process.
Continuously run with above steps, stably produce qualified products.
Embodiment five
A kind of method of hydrometallurgy metal nickel cobalt and its salt product, comprises the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Outsourcing cobalt salt class raw material is selected as nickel cobalt raw material, by outsourcing cobalt salt class Raw material uses sulfuric acid leaching after carrying out pulp, obtains the sulphuric leachate that pH is 1~2.5, contains Co in solution2+：45g/L、Ni2+： 1.2g/L、Fe2+：3.7g/L、Mn2+：2.6g/L、Cu2+：The metal ions such as 2.9g/L.
(2) step (1) resulting solution is subjected to copper removal, LIX extractants extract copper removal, and solution cupric is down to after copper removal 0.2g/L。
(3) oxidation of black cobalt cobalt slag or sodium chlorate is added in the solution obtained to step (2) and removes cobalt, the cobalt in solution is with Co (OH)3Sedimentation, makes to contain cobalt≤0.01g/L in solution, concentration of cobalt ions reaches 43.5g/L in solution, and filtering solution obtains solid-state Black cobalt slag.
(4) the high cobalt liquor for obtaining step (2), electrowinning with insoluble anode is carried out, negative electrode, cathode-current density are done with titanium plate 300~350A/m2, obtain thick cobalt metal derby, thick cobalt block containing total impurities such as cobalt >=97%, cupric≤1%, iron and manganese≤ 0.5%.
(5) in the continuous electrolytic deposition process of step (4), solution is in step (1) leaching process and the continuous electrolytic deposition process of step (4) Circulation, solution pH after step (4) electrodeposition are down to 0.5~1, return to step (1) and leached, leachate removes through step (2) again After copper, make cobalt copper ratio >=10 in solution, now solution returns to step (4) continuous electrodeposition again.
(6) as acid ion >=200g/L in the low cobalt solution that step (4) obtains, after carbonate precipitation cobalt, then pass through After ion exchange depth recovery valuable metal, waste liquid send waste water station to handle.
(7) the thick cobalt metal derby that step (4) obtains does anode, is put into after scrubbed in sulfuric acid or hydrochloric acid system, diel System keeps highly acidity, and hydrogen ion concentration >=1.5g/L, cobalt dissolves in the solution in the form of divalent ion, and it is low miscellaneous molten to obtain high cobalt Liquid.
Continuously run with above steps, stably produce qualified products.
The present invention and embodiments thereof are described above, this description is no restricted, and the present invention does not limit to In this, all in all if one of ordinary skill in the art is enlightened by it, without departing from the spirit of the invention, The scheme similar to the present invention program is designed without creativeness, protection scope of the present invention all should be belonged to.

Claims (9)

1. a kind of method of hydrometallurgy metal nickel cobalt and its salt product, it is characterised in that comprise the following steps：
(1) sulfuric acid leaching is carried out to nickel cobalt raw material：Sulfuric acid leaching is carried out to nickel cobalt raw material and forms leaching system, gained leachate is Containing cobalt, copper, nickel, iron, zinc, lead, manganese, chromium different kinds of ions sulfuric acid mixed salt solution.
(2) electrodeposition is carried out by raw material of sulphuric leachate：Electrodeposition is carried out by raw material of the sulfuric acid mixed salt solution that step (1) obtains Electrodeposition system is formed, electrodeposition anode uses the insoluble anode under sulfuric acid system, and electrodeposition negative electrode uses titanium net, titanium plate or stainless steel plate Deng conductive metallic material, under the conditions of electrodeposition, the element based on the metal ions such as the higher copper of electrode potential, nickel, cobalt is in the moon Pole separates out to form metallic monolith negative electrode, and anode reaction releases oxygen and produces H+。
(3) solution circulates：In step (2) electrolytic deposition process, solution acidity rise, electrodeposition system acidity higher solution and raw material The solution of sulfuric acid leaching system is circulating system, and solution goes step (1) leaching system to supplement main grade again when electrodeposition acidity raises Concentration of metal ions, acidity reduces and goes step (2) electrodeposition system again after leaching.
(4) impurity is separated：Step (3) solution electrodeposition and leach cyclic process in, the low impurity of manganese, zinc, ferroelectricity electrode potential into Part concentration constantly raises, and as impurity total concentration >=20g/L, liquid is stand-by after periodically extracting the electrodeposition of certain volume out, and supplements new Leachate, foreign ion total concentration≤80g/L in solution recycle system is kept, electrodeposition and leaching cyclic process is not formed knot Brilliant, negative electrode separates out product based on main grade cobalt.
(5) liquid after the electrodeposition that step (4) is extracted out, using in liquid after chemical precipitation method, ion-exchange or extraction recovery electrodeposition Copper, nickel, the valuable metal such as cobalt, reclaim the valuable metal come and be again introduced into production system, impure waste water from process is leached Remove Waste Water Treatment.
(6) metallic nickel, cobalt are produced：The cathode block using metal nickel cobalt as main grade that step (2) obtains, is put into refining after scrubbed Make anode in chlorination system electrolytic cell, produced using diaphragm electrolysis or electrolysis with ion-exchange film technique productions high pure metal nickel cobalt and its salt Product.
(7) in step (2) electrolytic deposition process, the higher metal ion of electrode potential preferentially separates out in solution, by controlling electrodeposition mistake The tank voltage of journey, make the precipitation voltage of the tank voltage impurity element low less than electrode potential, this foreign ion electricity not on negative electrode Product separates out, and reaches the purpose of isolation of purified purification.
(8) in step (2) electrolytic deposition process, the higher metal ion of electrode potential preferentially separates out in solution, by controlling electrodeposition mistake Journey cathode-current density≤380A/m2, solution temperature >=45 DEG C, solution flow through linear velocity >=0.1m/s of cathode surface, electrode The higher metal ion of potential is supplemented and preferentially separated out in time in cathode surface, as main grade concentration of metal ions >=5g/L When, impurity content≤10% of precipitation, as main grade concentration of metal ions≤5g/L, the impurity content of precipitation≤ 20%.
(9) step (6) refining process Anodic liquid enters after the mode deep purifying such as extraction or chemical precipitation, ion exchange Cathodic region supplements main grade concentration of metal ions.
2. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute Main grade nickel or concentration of cobalt ions >=5g/L in leachate obtained by step (1) are stated, the pH value of leachate is controlled 0~4.0.
3. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute The pH value for stating circulating system solution in step (2) is controlled 0~4.0.
4. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Step Suddenly cobalt grade >=80% of (4) negative electrode output object.
5. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute It can be that sulfuric acid leaching, ammonia leach to state step (1) leaching system, or Cyanide Leaching, different Leaching Systems subsequent treatments The principle of process is identical.
6. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute State the copper of the sulphuric leachate also obtained between step (1) and step (2) including the use of extraction, displacement method separating step (1) Deng the high ion of electrode potential, avoid separating out the precipitation for forming the main grade composition of galvanic cell influence in electrolytic deposition process.
7. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute State in step (2) electrolytic deposition process, boric acid or Boratex are incorporated in solution.
8. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute State in step (2) electrolytic deposition process, using electrolytic cell constant voltage electrodeposition method, control electrodeposition tank voltage, electrodeposition voltage is made master Grade element separates out in negative electrode, with the reduction of main grade concentration of metal ions in solution, keeps tank voltage constant, DC current Reduce, the more negative impurity element of coordination electrode potential do not separate out largely, the amount of precipitation of foreign ion account for total amount of precipitation≤10%, As main grade concentration≤5g/L, the impurity element amount of precipitation account for total amount of precipitation≤20%.
9. the method for a kind of hydrometallurgy metal nickel cobalt according to claim 1 and its salt product, it is characterised in that：Institute Step (2) is stated in progress electrolytic deposition process in the case of sulfuric acid, nitric acid, hydrochloric acid, ammonia or complex or the mixing of a variety of systems, sun Pole electrochemical reaction can release oxygen, can also separate out corresponding oxidation product according to solution compolision situation.
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CN116768430B (en) * 2023-08-24 2023-10-27 纬景储能科技有限公司 Alkaline electrolyte treatment method and system

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