CN114408978A - Process for preparing battery-grade manganese sulfate by using manganese in cobalt raw material - Google Patents
Process for preparing battery-grade manganese sulfate by using manganese in cobalt raw material Download PDFInfo
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- CN114408978A CN114408978A CN202210216320.5A CN202210216320A CN114408978A CN 114408978 A CN114408978 A CN 114408978A CN 202210216320 A CN202210216320 A CN 202210216320A CN 114408978 A CN114408978 A CN 114408978A
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- manganese
- ions
- solution system
- raw material
- manganese sulfate
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 26
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 26
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 26
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 20
- 239000011572 manganese Substances 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 19
- 229910001431 copper ion Inorganic materials 0.000 claims description 19
- 229910001424 calcium ion Inorganic materials 0.000 claims description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 235000006748 manganese carbonate Nutrition 0.000 claims description 9
- 239000011656 manganese carbonate Substances 0.000 claims description 9
- 229940093474 manganese carbonate Drugs 0.000 claims description 9
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 9
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- -1 hydrogen ions Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/04—Combinations of filters with settling tanks
Abstract
The invention discloses a process for preparing battery-grade manganese sulfate by using manganese in a cobalt raw material, wherein only manganese ions are introduced in the whole process, so that secondary pollution to a solution system is avoided, high-purity manganese sulfate is prepared, the complexity of subsequent treatment is not improved, and the purification cost is reduced; the invention also carries out on-line separation on the solid-phase precipitate generated in the precipitation reaction by the circulating separation device, thereby reducing the concentration of the reactant in the solution system, promoting the precipitation reaction, improving the precipitation efficiency on one hand, leading the precipitation reaction to be carried out more thoroughly on the other hand, and being beneficial to removing impurity ions in the solution system.
Description
Technical Field
The invention belongs to the field of hydrometallurgical metals, and particularly relates to a process for preparing battery-grade manganese sulfate from manganese in a cobalt raw material.
Background
With the development of the lithium battery industry, the demand of battery-grade manganese sulfate required by the ternary lithium battery is greatly increased, and the cobalt raw material contains manganese with a high proportion, so that after the cobalt is produced and purified, the manganese can be purified and utilized by using reaction byproducts of the cobalt, the production benefit is improved, and the utilization efficiency of resources is improved;
the method comprises the steps of carrying out one-by-one precipitation treatment on main components such as calcium ions, zinc ions and copper ions in the liquid phase by-product to obtain a relatively pure liquid phase component containing a large amount of manganese ions, and then carrying out enrichment, recovery and purification on the manganese ions to obtain the battery-grade manganese sulfate meeting the requirements, but the method has the problems that the generally obtained manganese-rich solution system contains more impurity ions, the precipitation is incomplete, the subsequent manganese treatment and purification difficulty is high, the cost is high, and in order to solve the problems, the invention provides the following technical scheme.
Disclosure of Invention
The invention aims to provide a process for preparing battery-grade manganese sulfate by using manganese in a cobalt raw material, and solves the problems that in the prior art, a manganese-rich solution system has more impurity ions and incomplete precipitation, so that the subsequent treatment cost is higher.
The purpose of the invention can be realized by the following technical scheme:
a process for preparing battery-grade manganese sulfate by using manganese in a cobalt raw material comprises the following steps;
s1, precipitating and removing copper ions, calcium ions and heavy metal ions in a liquid phase generated in the cobalt raw material processing process to obtain a manganese-rich solution;
in the process of precipitating copper ions, calcium ions and heavy metal ions, carrying out online separation on a solid phase and a liquid phase through a circulating separation device, and stopping the circulating separation device to carry out solid-liquid separation on a solution system when the concentration of free ions to be removed in the solution system is reduced to a preset value;
s2, dropwise adding concentrated sulfuric acid into the solution system, wherein the dosage of the concentrated sulfuric acid is 0.95-1.95 times of the molar weight of manganese ions in the solution system, after the dropwise adding of the concentrated sulfuric acid is finished, maintaining the reaction temperature at 90-95 ℃, stirring for reaction for 1-2.5 hours, and crystallizing and purifying the obtained manganese sulfate to obtain the battery-grade manganese sulfate.
As a further scheme of the invention, the method for removing the copper ions comprises the following steps: heating the liquid phase to 55-65 deg.C, adding manganese carbonate with a dosage of 0.3-0.5 mol% of free hydrogen ions in the solution system, and maintaining the pH value of the solution system at 2.5-3.5 during the addition of manganese carbonate and/or zinc carbonate.
As a further scheme of the invention, the method for removing calcium ions comprises the following steps: adding manganese sulfate into the solution system with the temperature of 25-35 ℃ and removing copper ions, and stirring, mixing and dissolving.
As a further scheme of the invention, after the calcium ions and the copper ions are removed, the solution system is heated to 80-90 ℃, and then manganese sulfide is added into the solution system.
As a further scheme of the invention, the circulating separation device comprises a reaction kettle, the bottom of the reaction kettle is connected with one end of a circulating pipe, the other end of the circulating pipe is connected with the top of the reaction kettle, the circulating pipe is connected with a filter pipe, and the liquid inlet end of the filter pipe is provided with a valve;
the filter pipe comprises an upper conduction pipe and a lower conduction pipe, wherein a filter screen is arranged between the upper conduction pipe and the lower conduction pipe, the filter screen comprises a screen part and a seal ring arranged on the edge of the screen part, and the size and the position of the seal ring are arranged corresponding to the pipe diameter of the joint of the upper conduction pipe and the lower conduction pipe;
one position of the upper sealing ring of the filter screen is hinged with the side wall of the uploading conduit, and the filter screen can rotate around a hinged point;
the lower conducting pipe can be driven to reciprocate in the vertical direction.
As a further proposal of the invention, the circulating pipe is connected with two filter pipes which are arranged in parallel and work alternately in a mode of filtering and deslagging.
As a further aspect of the present invention, the filter mesh screen is connected to a hinge connection device, which is fixedly installed on a sidewall of the upper conduction pipe;
the hinged connection device comprises a positioning device fixedly arranged on the pipe wall of the upper conduction pipe and a connecting piece arranged in the positioning device in a sliding manner;
the one end of positioner is kept away from to the connecting piece rotates the one end of installing the articulated connecting rod, and the other end and the sealing washer fixed connection of articulated connecting rod are provided with driving motor drive filter screen on the connecting piece and sieve and rotate.
As a further scheme of the present invention, the lower conducting tube includes a lifting substrate, a pipeline structure is fixedly mounted on the lifting substrate, the pipeline structure penetrates through the lifting substrate, an outer wall of the pipeline structure is fixedly connected to the lifting substrate, one part of the pipeline structure is located above the lifting substrate and used for being abutted to the upper conveying pipe, the other part of the pipeline structure is located below the lifting substrate and used for being connected to the hose, and the lifting substrate is driven by a lifting driving cylinder to reciprocate in a vertical direction.
As a further scheme of the invention, the circulating separation device also comprises a baffle plate arranged on one side of the lower conduction pipe, the baffle plate is horizontally arranged, the baffle plate is driven by a rotating motor to rotate in the horizontal direction, and after the lower conduction pipe moves downwards, the baffle plate rotates to the position above the lower conduction pipe to shield the pipe orifice of the lower conduction pipe.
The invention has the beneficial effects that:
(1) according to the method, copper ions are removed by introducing manganese carbonate into a solution system, calcium ions in the solution system are removed by introducing manganese sulfate, and residual trace heavy metal ions in the solution system are removed by introducing manganese sulfide, so that only manganese ions are introduced in the whole process, secondary pollution to the solution system is avoided, high-purity manganese sulfate can be prepared, the complexity of subsequent treatment is not improved, and the purification cost is reduced;
(2) according to the invention, the solid-phase precipitate generated in the precipitation reaction is separated on line by the circulating separation device, so that the concentration of the reactant in the solution system is reduced, the precipitation reaction is promoted, the precipitation efficiency is improved on one hand, the precipitation reaction is carried out more thoroughly on the other hand, and the removal of impurity ions in the solution system is facilitated;
(3) the circulation separation device filters a solution system passing through the pipeline automatically and transfers precipitated impurities generated by filtering in time, so that online continuous filtering treatment is realized, and normal operation of precipitation reaction is not influenced.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic view of the construction of the circulation separation apparatus of the present invention;
FIG. 2 is a schematic structural view of a filter tube according to the present invention;
FIG. 3 is a schematic structural view of a lower conductive pipe of the present invention;
fig. 4 is a schematic view of the construction of the hinge connecting device of the present invention.
In the figure: 1. a reaction kettle; 2. a filter tube; 11. a circulation pipe; 21. an uploading conduit; 22. a lower conducting tube; 23. filtering the mesh screen; 24. a hinged connection; 25. a baffle plate; 221. a pipe structure; 223. lifting the substrate; 224. lifting the driving cylinder; 231. a mesh screen section; 232. a seal ring; 241. a positioning device; 242. a connecting member; 243. a limiting bulge; 244. a limiting chute; 245. a hinged connection rod; 246. a drive motor; 247. a transmission gear; 248. a buffer spring; 251. a rotating electric machine.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A process for preparing battery-grade manganese sulfate by using manganese in a cobalt raw material comprises the following steps;
s1, precipitating and removing impurity ions such as copper ions and calcium ions in a liquid phase generated in the cobalt raw material processing process to obtain a manganese-rich solution;
the method for removing the copper ions comprises the following steps: heating a manganese-containing liquid phase generated in the processing process of a cobalt raw material to 55-65 ℃, then adding manganese carbonate into the liquid phase, wherein the dosage of the manganese carbonate is 0.3-0.5 of the molar weight of free hydrogen ions in a solution system, the manganese carbonate is added into the solution system in 3-5 equal parts in sequence, the pH value of the solution system is kept to be 2.5-3.5 in the process of adding the manganese carbonate and/or zinc carbonate, and the precipitation time of copper ions is 1-2.5 h;
the method for removing calcium ions comprises the following steps: adding manganese sulfate into the solution system with the temperature of 25-35 ℃ and copper ions removed, stirring, mixing and dissolving, wherein the use amount of the manganese sulfate is 2-4 times of the molar amount of free calcium ions in the solution system, and the precipitation time of the calcium ions is 1.5-2 h;
after the calcium ions and the copper ions are removed, heating the solution system to 80-90 ℃, and then adding manganese sulfide into the solution system, wherein the use amount of the manganese sulfide is 1-1.2 times of the molar amount of free heavy metal ions in the solution system, and the precipitation time of the heavy metal ions is 1.5-2 hours;
wherein the heavy metal ions comprise copper ions, zinc ions, cobalt ions, lead ions, nickel ions and the like;
in the process of precipitating copper ions, calcium ions and heavy metal ions, a solid phase and a liquid phase are separated on line through a circulating separation device, so that precipitation is promoted, and when the concentration of free ions to be removed in a solution system is reduced to a preset value, the solution system is thoroughly filtered once;
s2, dropwise adding concentrated sulfuric acid into the solution system, wherein the use amount of the concentrated sulfuric acid is 0.95-1.95 times of the molar amount of manganese ions in the solution system, after the dropwise adding of the concentrated sulfuric acid is finished, maintaining the reaction temperature at 90-95 ℃, stirring for reaction for 1-2.5 hours, and crystallizing and purifying the obtained manganese sulfate to obtain battery-grade manganese sulfate;
wherein the crystallization purification is five-stage countercurrent series recrystallization.
As shown in fig. 1 to 4, the circulation separation device comprises a reaction kettle 1, wherein the bottom of the reaction kettle 1 is connected with one end of a circulation pipe 11, the other end of the circulation pipe 11 is connected with the top of the reaction kettle 1, the circulation pipe 11 is connected with a filter pipe 2, and the liquid inlet end of the filter pipe 2 is provided with a valve;
preferably, the circulating pipe 11 is connected with two filtering pipes 2 which are arranged in parallel, and the two filtering pipes 2 alternately work in a filtering-deslagging mode to realize continuous on-line filtering;
the filter pipe 2 comprises an upper guide pipe 21 and a lower guide pipe 22, wherein a filter screen 23 is arranged between the upper guide pipe 21 and the lower guide pipe 22, the filter screen 23 comprises a screen part 231 and a sealing ring 232 arranged on the edge of the screen part 231, and the size and the position of the sealing ring 232 are arranged corresponding to the pipe diameter of the joint of the upper guide pipe 21 and the lower guide pipe 22;
the lower conduction pipe 22 can be driven to reciprocate in the vertical direction, so that the filter screen 23 is clamped and a space is provided for the rotation of the filter screen 23;
preferably, a layer of sealing rubber is arranged on the upper end face and the lower end face of the sealing ring 232, so that the effects of buffering and improving the sealing effect can be achieved;
one position of the upper sealing ring 232 of the filtering mesh 23 is hinged with the side wall of the upper conveying pipe 21, so that the filtering mesh 23 can rotate around the hinged point;
in one embodiment of the present invention, the filter screen 23 is connected with a hinge connection 24, the hinge connection 24 is fixedly installed on a sidewall of the upper conducting pipe 21;
the hinge connection device 24 comprises a positioning device 241 fixedly mounted on the pipe wall of the upper conduction pipe 21 and a connecting piece 242 slidably mounted in the positioning device 241, a limiting sliding groove 244 is arranged in the positioning device 241, and a limiting protrusion 243 is arranged at one end of the connecting piece 242 in the limiting sliding groove 244, so that the connecting piece 242 cannot be separated from the limiting sliding groove 244 and can slide in the limiting sliding groove 244 in a certain range along the vertical direction;
in one embodiment of the present invention, a buffer spring 248 is connected between the top of the connecting member 242 and the top of the limiting chute 244;
one end of the connecting piece 242, which is far away from the positioning device 241, is rotatably provided with one end of a hinged connecting rod 245, the other end of the hinged connecting rod 245 is fixedly connected with the sealing ring 232, one end of the rotating shaft of the hinged connecting rod 245 is fixedly sleeved with a transmission gear 247, the connecting piece 242 is also fixedly provided with a driving motor 246, and the driving motor 246 drives the transmission gear 247 to rotate so as to drive the filter screen 23 to rotate, so that solid-phase precipitates in the filter screen 23 can be conveniently removed;
in an embodiment of the present invention, the lower conducting pipe 22 includes a lifting base plate 223, the lifting base plate 223 is fixedly provided with a pipe structure 221, specifically, the pipe structure 221 penetrates through the lifting base plate 223, an outer wall of the pipe structure 221 is fixedly connected to the lifting base plate 223, a part of the pipe structure 221 is located above the lifting base plate 223 and is used for being abutted to the upper conducting pipe 21, another part of the pipe structure 221 is located below the lifting base plate 223 and is used for being connected to a hose, and the lifting base plate 223 is driven by a lifting driving cylinder 224 to reciprocate in a vertical direction;
in an embodiment of the present invention, the circulation separation apparatus further includes a baffle 25 disposed at one side of the lower conduction pipe 22, the baffle 25 is disposed horizontally, the baffle 25 can be driven by the rotating motor 251 to rotate in the horizontal direction, and when the lower conduction pipe 22 moves downward to provide a space for the rotation of the filter screen 23, the baffle 25 rotates to above the lower conduction pipe 22 to shield the nozzle of the lower conduction pipe 22, so as to prevent the solid phase filtrate in the filter screen 23 from falling into the lower conduction pipe 22 when the filter screen 23 rotates, and the filtering effect is not affected.
The circulation separation device can continuously filter and separate solid-phase precipitates in the precipitation process on line, and precipitate products are discharged in time, so that the precipitation reaction is promoted to be carried out, the precipitation is more sufficient and thorough, and the precipitation efficiency is higher.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (4)
1. A process for preparing battery-grade manganese sulfate by using manganese in a cobalt raw material is characterized by comprising the following steps;
s1, precipitating and removing copper ions, calcium ions and heavy metal ions in a liquid phase generated in the cobalt raw material processing process to obtain a manganese-rich solution;
in the process of precipitating copper ions, calcium ions and heavy metal ions, carrying out online separation on a solid phase and a liquid phase through a circulating separation device, and stopping the circulating separation device to carry out solid-liquid separation on a solution system when the concentration of free ions to be removed in the solution system is reduced to a preset value;
s2, dropwise adding concentrated sulfuric acid into the solution system, wherein the dosage of the concentrated sulfuric acid is 0.95-1.95 times of the molar weight of manganese ions in the solution system, after the dropwise adding of the concentrated sulfuric acid is finished, maintaining the reaction temperature at 90-95 ℃, stirring for reaction for 1-2.5 hours, and crystallizing and purifying the obtained manganese sulfate to obtain the battery-grade manganese sulfate.
2. The process for preparing battery-grade manganese sulfate from manganese in cobalt raw material as claimed in claim 1, wherein the method for removing copper ions comprises: heating the liquid phase to 55-65 deg.C, adding manganese carbonate in an amount of 0.3-0.5 times of the molar amount of free hydrogen ions in the solution system, and maintaining the pH value of the solution system at 2.5-3.5 during the addition of manganese carbonate and/or zinc carbonate.
3. The process for preparing battery-grade manganese sulfate from manganese in cobalt raw material as claimed in claim 2, wherein the method for removing calcium ions comprises: adding manganese sulfate into the solution system with the temperature of 25-35 ℃ and removing copper ions, and stirring, mixing and dissolving.
4. The process for preparing battery-grade manganese sulfate from manganese in cobalt raw material as claimed in claim 3, wherein after the removal of calcium and copper ions is completed, the solution system is heated to 80-90 ℃, and then manganese sulfide is added.
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CN210252287U (en) * | 2019-07-12 | 2020-04-07 | 杭州赫尔伯生物科技有限公司 | A purification separation all-in-one for HCG |
CN113716613A (en) * | 2020-05-25 | 2021-11-30 | 四川沃林山水环保科技有限公司 | Preparation method of high-purity manganese sulfate |
CN213101166U (en) * | 2020-08-18 | 2021-05-04 | 宁夏睿源石油化工有限公司 | Material circulating filter device |
CN112499686A (en) * | 2020-12-18 | 2021-03-16 | 杜长福 | Method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid |
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