CN110127766A - A kind of preparation process of LITHIUM BATTERY manganese sulfate solution - Google Patents
A kind of preparation process of LITHIUM BATTERY manganese sulfate solution Download PDFInfo
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- CN110127766A CN110127766A CN201910587886.7A CN201910587886A CN110127766A CN 110127766 A CN110127766 A CN 110127766A CN 201910587886 A CN201910587886 A CN 201910587886A CN 110127766 A CN110127766 A CN 110127766A
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 49
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 49
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 49
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 13
- 239000011028 pyrite Substances 0.000 claims abstract description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 235000010755 mineral Nutrition 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 23
- 230000001376 precipitating effect Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 6
- RTTCFFTVCUNXLX-UHFFFAOYSA-N n,n-di(octan-2-yl)acetamide Chemical compound CCCCCCC(C)N(C(C)=O)C(C)CCCCCC RTTCFFTVCUNXLX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000001223 reverse osmosis Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000027089 Parkinsonian disease Diseases 0.000 description 1
- 206010034010 Parkinsonism Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- AZMQGJINSTTZTP-UHFFFAOYSA-J manganese(2+);disulfate Chemical compound [Mn+2].[Mn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AZMQGJINSTTZTP-UHFFFAOYSA-J 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009251 neurologic dysfunction Effects 0.000 description 1
- 208000015015 neurological dysfunction Diseases 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation processes of LITHIUM BATTERY manganese sulfate solution, include the following steps: step 1: pyrolusite and pyrite are respectively weighed 15-25 kilograms after the crushing of mineral breaker device respectively, carry out mixing 10-20 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after 20-40 minutes to be leached, and manganese sulfate solution is obtained.The technique that the present invention prepares manganese sulfate is prepared using wet process, and operating process will not generate pollution, and production process is relatively simple, labor intensity is reduced, and the utilization rate of manganese is high, reduces the waste of energy consumption and resource, the preparation process of existing manganese sulfate is solved using high-temperature roasting method, but the process of this preparation process is longer, and it is slight big to work, environmental pollution is more serious, and the utilization rate of manganese is very low, the problem of energy consumption of waste is more, waste of resource is suitble to industrialized mass production.
Description
Technical field
The invention belongs to technical field of lithium batteries, more particularly to a kind of preparation process of LITHIUM BATTERY manganese sulfate solution.
Background technique
Manganese sulfate, monohydrate are blush rhomboidal crystal, and relative density 3.50, fusing point is 700 DEG C, is soluble in
Water does not dissolve in ethyl alcohol, exists in the form of a variety of hydrates, and manganese sulfate is the micro member that the crop of synthetic fatty acid needs
Element, therefore manganese sulfate can be applied as fertilizer into soil, can be increased production.Manganese sulfate is added in animal feed, there is the effect of fattening.
Manganese sulfate is also the raw material and analytical reagent for preparing other manganese salts, in the industrial productions such as electrolytic manganese, dyestuff, papermaking and ceramics
Also manganese sulfate is used, because easily deliquescing, the scope of application is restricted.Manganese sulfate is non-ignitable, has irritation.Sucking, intake or warp
Skin absorbs harmful, tool stimulation.The product dust is sucked for a long time, can cause Chronic Mn Poisoning, in early days with neurasthenic syndrome
Based on neurological dysfunction, there is Parkinsonism in advanced stage, harmful to environment, can pollute to water body.
Manganese sulfate is wide application to be obtained in light, electricity, the preparation of magnetic system material, due to LITHIUM BATTERY with a kind of manganese salt
Manganese sulfate requires impurity very harsh, it is necessary to potassium, sodium, calcium, magnesium and the huge sum of money that strict control is affected to lithium ion battery
The impurity contents such as belong to, and the preparation process of existing manganese sulfate uses high-temperature roasting method, but the process of this preparation process compared with
It is long, and it is slight big to work, and environmental pollution is more serious, and the utilization rate of manganese is very low, and the energy consumption of waste is more, waste money
Source.
Summary of the invention
The object of the present invention is to provide a kind of preparation processes of LITHIUM BATTERY manganese sulfate solution, are prepared using wet process, behaviour
The process of work will not generate pollution, and production process is relatively simple, reduce labor intensity, and the utilization rate of manganese is done, and energy is reduced
The waste of consumption and resource, to solve manganese sulfate preparation process in above-mentioned background technique.
The technical scheme to solve the above technical problems is that a kind of preparation process of LITHIUM BATTERY manganese sulfate solution,
Include the following steps:
Step 1: pyrolusite and pyrite are respectively weighed 15-25 kilograms after the crushing of mineral breaker device respectively, carried out
Mixing 10-20 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after 20-40 minutes to be leached, and is obtained
Manganese sulfate solution；
Step 2: being added dilute hydrochloric acid into the compounding substances after leaching, is stirred when being added dropwise to mixed material, and
Mixture is heated, after being all added dropwise to complete, continue stirring 10-15 minute, stirring after the completion continue it is 5-8 minutes static,
Solid precipitating in mixture is waited to keep stablizing；
Step 3: continuing the addition fluoride into mixing liquid and carry out Precipitation to the heavy metal ion in mixture,
The time of precipitating is 1-2 hours；
Step 4:, by static 30-50 minutes cooling, thick mistake will be carried out to mixed material using filter screen after precipitating
Filter, filter residue carry out filters pressing by filtering equipment, the solution in filter residue are filtered out, 2-5 after filter cake is washed repeatedly by deionized water
It is secondary, filters pressing is carried out again, and the pure water or deionized water that filtrate is obtained by RO reverse osmosis membrane filtration first impregnate 10-20min, then will
Water filters off, and repetitive operation 2-3 times obtains slightly vulcanizing manganese solution；
Step 5: extractant is added into filtered filtrate and diluent extracts filtrate, obtains refined sulfuric acid
Manganese solution；
Step 6: obtained refined sulfuric acid manganese solution is filtered, and filtered solution is by being concentrated by evaporation, cooling knot
Crystalline substance obtains LITHIUM BATTERY manganese sulfate.
The present invention uses the preparation process of LITHIUM BATTERY manganese sulfate solution described above, further, pyrolusite in step 1
Passing through smashed grain diameter size with pyrite is 300-500 mesh, and smashed particle passes through drying machine drying 20-
40 minutes, except the moisture in degranulation.
The present invention uses the preparation process of LITHIUM BATTERY manganese sulfate solution described above, further, making in the step 1
The mass fraction of the dilute hydrochloric acid used in sulfuric acid and step 2 is respectively 65-80% and 9.2-10.2.
The present invention uses the preparation process of LITHIUM BATTERY manganese sulfate solution described above, further, the step 1 and step
Rapid two operation is arranged under 50-65 degrees Celsius and carries out, dilute hydrochloric acid be added during with 10-15Kg speed hourly into
Row addition.
The present invention uses the preparation process of LITHIUM BATTERY manganese sulfate solution described above, further, to filter in step 4
After liquid extraction, the pH value of manganese hydrogen sodium regulating solution is added into solution, is existed using soda acid tester detection solution pH value
Between 6.5-8.5.
The present invention uses the preparation process of LITHIUM BATTERY manganese sulfate solution described above, further, the extractant is N,
One of N- dioctyl -1- octylame and N, N- bis- (1- methylheptyl) acetamide；The diluent is kerosene and atoleine
One of.
The present invention uses the preparation process of LITHIUM BATTERY manganese sulfate solution described above, further, the step 6 filters
The filter device filter diameter size used is operated as 5-15 mesh.
The beneficial effects of the present invention are: the technique that the present invention prepares manganese sulfate is prepared using wet process, operating process is not
Pollution can be generated, production process is relatively simple, reduces labor intensity, and the utilization rate of manganese is high, reduces energy consumption and resource
Waste, the preparation process for solving existing manganese sulfate uses high-temperature roasting method, but the process of this preparation process is longer, and
And labour is slight big, environmental pollution is more serious, and the utilization rate of manganese is very low, and the energy consumption of waste is more, and waste of resource is asked
Topic is suitble to industrialized mass production.
Specific embodiment
Hereinafter, by the embodiment of the preparation process referring to LITHIUM BATTERY manganese sulfate solution of the invention.
The embodiment recorded herein is specific specific embodiment of the invention, for illustrating design of the invention,
Be it is explanatory and illustrative, should not be construed as the limitation to embodiment of the present invention and the scope of the invention.Except what is recorded herein
Outside embodiment, those skilled in the art can also based on the claim of this application book and specification disclosure of that using aobvious and
The other technical solutions being clear to, these technical solutions include using any obvious to making for the embodiment recorded herein
The technical solution of substitutions and modifications.
This specification aids in illustrating design of the invention, it is schematically indicated the shape and its correlation of each section.
A kind of preparation process of LITHIUM BATTERY manganese sulfate solution of an embodiment of the present invention, includes the following steps:
Step 1: pyrolusite and pyrite are respectively weighed 15-25 kilograms after the crushing of mineral breaker device respectively, carried out
Mixing 10-20 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after 20-40 minutes to be leached, and is obtained
Manganese sulfate solution, pyrolusite and pyrite are 300-500 mesh by smashed grain diameter size in step 1, after crushing
Particle pass through drying machine drying 20-40 minutes, except the moisture in degranulation；
Step 2: being added dilute hydrochloric acid into the compounding substances after leaching, is stirred when being added dropwise to mixed material, and
Mixture is heated, after being all added dropwise to complete, continue stirring 10-15 minute, stirring after the completion continue it is 5-8 minutes static,
Solid precipitating in mixture is waited to keep stablizing, the quality point of the dilute hydrochloric acid used in sulfuric acid used in step 1 and step 2
Number is respectively 65-80% and 9.2-10.2, and the operation of step 1 and step 2 is arranged under 50-65 degrees Celsius and carries out, dilute salt
Acid is added during being added with 10-15Kg speed hourly；
Step 3: continuing the addition fluoride into mixing liquid and carry out Precipitation to the heavy metal ion in mixture,
The time of precipitating is 1-2 hours；
Step 4:, by static 30-50 minutes cooling, thick mistake will be carried out to mixed material using filter screen after precipitating
Filter, filter residue carry out filters pressing by filtering equipment, the solution in filter residue are filtered out, 2-5 after filter cake is washed repeatedly by deionized water
It is secondary, filters pressing is carried out again, and the pure water or deionized water that filtrate is obtained by RO reverse osmosis membrane filtration first impregnate 10-20min, then will
Water filters off, and repetitive operation 2-3 times obtains slightly vulcanizing manganese solution, in step 4 after extracting to filtrate, carbon is added into solution
Sour hydrogen sodium adjusts the pH value of solution, using soda acid tester detection solution pH value between 6.5-8.5；
Step 5: extractant is added into filtered filtrate and diluent extracts filtrate, obtains refined sulfuric acid
Manganese solution；
Step 6: obtained refined sulfuric acid manganese solution is filtered, and filtered solution is by being concentrated by evaporation, cooling knot
Crystalline substance, obtains LITHIUM BATTERY manganese sulfate, and one in extractant N, N- dioctyl -1- octylame and N, N- bis- (1- methylheptyl) acetamide
Kind；Diluent be one of kerosene and atoleine, the filter device filter diameter size that step 6 filter operation uses for
5-15 mesh.
Embodiment one:
A kind of preparation process of LITHIUM BATTERY manganese sulfate solution, includes the following steps:
Step 1: pyrolusite and pyrite are respectively weighed 15 kilograms after the crushing of mineral breaker device respectively, mixed
It closes 10 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after twenty minutes to be leached, and it is molten to obtain manganese sulfate
Liquid, pyrolusite and pyrite are 300 mesh by smashed grain diameter size, and smashed particle is dried by dryer
It is 20 minutes dry, except the moisture in degranulation；
Step 2: being added dilute hydrochloric acid into the compounding substances after leaching, is stirred when being added dropwise to mixed material, and
Mixture is heated, after being all added dropwise to complete, continues stirring 10 minutes, continues static 5 minutes after the completion of stirring, wait mixed
It closes solid precipitating in object to keep stablizing, the mass fraction of the dilute hydrochloric acid of use is respectively 65% and 9.2, and operation temperature is arranged at
It is carried out under 50 degrees Celsius, dilute hydrochloric acid is added during being added with 10Kg speed hourly；
Step 3: continuing the addition fluoride into mixing liquid and carry out Precipitation to the heavy metal ion in mixture,
The time of precipitating is 1 hour；
Step 4:, by static cooling 30 minutes, coarse filtration, filter will be carried out to mixed material using filter screen after precipitating
Slag by filtering equipment carry out filters pressing, the solution in filter residue is filtered out, filter cake by deionized water wash repeatedly after 2 times, again
Filters pressing is carried out, the pure water or deionized water that filtrate is obtained by RO reverse osmosis membrane filtration first impregnate 10-20min, then water is filtered off,
It repetitive operation 2 times, obtains slightly vulcanizing manganese solution, after extracting to filtrate, manganese hydrogen sodium regulating solution is added into solution
PH value, using soda acid tester detection solution pH value 6.5；
Step 5: extractant is added into filtered filtrate and diluent extracts filtrate, obtains refined sulfuric acid
Manganese solution；
Step 6: obtained refined sulfuric acid manganese solution is filtered, and filtered solution is by being concentrated by evaporation, cooling knot
Crystalline substance, obtains LITHIUM BATTERY manganese sulfate, and one in extractant N, N- dioctyl -1- octylame and N, N- bis- (1- methylheptyl) acetamide
Kind；Diluent is one of kerosene and atoleine, and the filter device filter diameter size that filter operation uses is 5 mesh.
Embodiment two: the difference between this embodiment and the first embodiment lies in:
A kind of preparation process of LITHIUM BATTERY manganese sulfate solution, includes the following steps:
Step 1: pyrolusite and pyrite are respectively weighed 16 kilograms after the crushing of mineral breaker device respectively, mixed
It closes 15 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after twenty minutes to be leached, and it is molten to obtain manganese sulfate
Liquid, pyrolusite and pyrite are 350 mesh by smashed grain diameter size, and smashed particle is dried by dryer
It is 25 minutes dry, except the moisture in degranulation；
Step 2: being added dilute hydrochloric acid into the compounding substances after leaching, is stirred when being added dropwise to mixed material, and
Mixture is heated, after being all added dropwise to complete, continues stirring 15 minutes, continues static 8 minutes after the completion of stirring, wait mixed
It closes solid precipitating in object to keep stablizing, the mass fraction of the dilute hydrochloric acid of use is respectively 705% and 10, and operation temperature is arranged at
It is carried out under 50 degrees Celsius, dilute hydrochloric acid is added during being added with 12Kg speed hourly；
Step 3: continuing the addition fluoride into mixing liquid and carry out Precipitation to the heavy metal ion in mixture,
The time of precipitating is 1.5 hours；
Step 4:, by static cooling 35 minutes, coarse filtration, filter will be carried out to mixed material using filter screen after precipitating
Slag by filtering equipment carry out filters pressing, the solution in filter residue is filtered out, filter cake by deionized water wash repeatedly after 2 times, again
Filters pressing is carried out, the pure water or deionized water that filtrate is obtained by RO reverse osmosis membrane filtration first impregnate 10-20min, then water is filtered off,
It repetitive operation 3 times, obtains slightly vulcanizing manganese solution, after extracting to filtrate, manganese hydrogen sodium regulating solution is added into solution
PH value, using soda acid tester detection solution pH value 7；
Step 5: extractant is added into filtered filtrate and diluent extracts filtrate, obtains refined sulfuric acid
Manganese solution；
Step 6: obtained refined sulfuric acid manganese solution is filtered, and filtered solution is by being concentrated by evaporation, cooling knot
Crystalline substance, obtains LITHIUM BATTERY manganese sulfate, and one in extractant N, N- dioctyl -1- octylame and N, N- bis- (1- methylheptyl) acetamide
Kind；Diluent is one of kerosene and atoleine, and the filter device filter diameter size that filter operation uses is 8 mesh.
Embodiment three: the present embodiment and the difference of embodiment one and embodiment two are:
A kind of preparation process of LITHIUM BATTERY manganese sulfate solution, includes the following steps:
Step 1: pyrolusite and pyrite are respectively weighed 25 kilograms after the crushing of mineral breaker device respectively, mixed
It closes 20 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after forty minutes to be leached, and it is molten to obtain manganese sulfate
Liquid, pyrolusite and pyrite are 500 mesh by smashed grain diameter size in step 1, and smashed particle passes through
Drying machine drying 40 minutes, except the moisture in degranulation；
Step 2: being added dilute hydrochloric acid into the compounding substances after leaching, is stirred when being added dropwise to mixed material, and
Mixture is heated, after being all added dropwise to complete, continues stirring 15 minutes, continues static 8 minutes after the completion of stirring, wait mixed
It closes solid precipitating in object to keep stablizing, the mass fraction difference of the dilute hydrochloric acid used in sulfuric acid used in step 1 and step 2
For 80% and 10.2, the operation of step 1 and step 2 is arranged under 65 degrees Celsius and carries out, dilute hydrochloric acid be added during with
15Kg speed hourly is added；
Step 3: continuing the addition fluoride into mixing liquid and carry out Precipitation to the heavy metal ion in mixture,
The time of precipitating is 2 hours；
Step 4:, by static cooling 50 minutes, coarse filtration, filter will be carried out to mixed material using filter screen after precipitating
Slag by filtering equipment carry out filters pressing, the solution in filter residue is filtered out, filter cake by deionized water wash repeatedly after 5 times, again
Filters pressing is carried out, the pure water or deionized water that filtrate is obtained by RO reverse osmosis membrane filtration first impregnate 20min, then water is filtered off, weight
It operates 3 times again, obtains slightly vulcanizing manganese solution, in step 4 after being extracted to filtrate, sodium bicarbonate is added into solution and adjusts
The pH value of solution, using soda acid tester detection solution pH value between 8.5；
Step 5: extractant is added into filtered filtrate and diluent extracts filtrate, obtains refined sulfuric acid
Manganese solution；
Step 6: obtained refined sulfuric acid manganese solution is filtered, and filtered solution is by being concentrated by evaporation, cooling knot
Crystalline substance, obtains LITHIUM BATTERY manganese sulfate, and one in extractant N, N- dioctyl -1- octylame and N, N- bis- (1- methylheptyl) acetamide
Kind；Diluent be one of kerosene and atoleine, the filter device filter diameter size that step 6 filter operation uses for
15 mesh.
Each technical characteristic of above-mentioned disclosure is not limited to disclosed and other feature combination, and those skilled in the art are also
Can carry out other combinations between each technical characteristic according to the purpose of invention, be subject to realize the present invention purpose.
Claims (7)
1. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution, which comprises the steps of:
Step 1: pyrolusite and pyrite are respectively weighed 15-25 kilograms after the crushing of mineral breaker device respectively, mixed
10-20 minutes, towards sulfuric acid is added in mixed mixed material, stirring is stood after 20-40 minutes to be leached, and obtained sulfuric acid
Manganese solution；
Step 2: being added dilute hydrochloric acid into the compounding substances after leaching, is stirred when being added dropwise to mixed material, and to mixed
It closes object to be heated, after being all added dropwise to complete, continues stirring 10-15 minutes, continue 5-8 minutes static, waiting after the completion of stirring
Solid precipitating keeps stablizing in mixture；
Step 3: continue to be added fluoride into mixing liquid to the heavy metal ion progress Precipitation in mixture, precipitating
Time be 1-2 hours；
Step 4:, by static 30-50 minutes cooling, coarse filtration, filter will be carried out to mixed material using filter screen after precipitating
Slag carries out filters pressing by filtering equipment, and the solution in filter residue is filtered out, and filter cake passes through after deionized water is washed repeatedly 2-5 times, then
Secondary carry out filters pressing, the pure water or deionized water that filtrate is obtained by RO reverse osmosis membrane filtration first impregnate 10-20min, then water is filtered
It goes, repetitive operation 2-3 times, obtains slightly vulcanizing manganese solution；
Step 5: extractant is added into filtered filtrate and diluent extracts filtrate, it is molten to obtain refined sulfuric acid manganese
Liquid；
Step 6: obtained refined sulfuric acid manganese solution is filtered, and filtered solution is by being concentrated by evaporation, crystallisation by cooling,
Obtain LITHIUM BATTERY manganese sulfate.
2. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution according to claim 1, which is characterized in that soft in step 1
It is 300-500 mesh that manganese ore and pyrite, which pass through smashed grain diameter size, and smashed particle passes through dryer and dries
It is 20-40 minutes dry, except the moisture in degranulation.
3. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution according to claim 1, which is characterized in that the step 1
Used in the mass fraction of dilute hydrochloric acid that uses in sulfuric acid and step 2 be respectively 65-80% and 9.2-10.2.
4. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution according to claim 1, it is characterised in that: the step 1
Operation with step 2 is arranged under 50-65 degrees Celsius and carries out, with 10-15Kg speed hourly during dilute hydrochloric acid addition
Degree is added.
5. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution according to claim 1, which is characterized in that in step 4
After filtrate extraction, the pH value of manganese hydrogen sodium regulating solution is added into solution, detects solution PH using soda acid tester
Value is between 6.5-8.5.
6. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution according to claim 1, which is characterized in that the extractant
For N, one of N- dioctyl -1- octylame and N, N- bis- (1- methylheptyl) acetamide；The diluent is kerosene and liquid
One of paraffin.
7. a kind of preparation process of LITHIUM BATTERY manganese sulfate solution according to claim 1, which is characterized in that the step 6
The filter device filter diameter size that filter operation uses is 5-15 mesh.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002717A (en) * | 1975-01-09 | 1977-01-11 | Deepsea Ventures, Inc. | Refining of manganese oxide ores |
| CN1311340A (en) * | 2000-02-28 | 2001-09-05 | 邓建成 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
| CN101337692A (en) * | 2008-08-21 | 2009-01-07 | 广西远辰锰业有限公司 | Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material |
| CN102212697A (en) * | 2011-05-18 | 2011-10-12 | 湖南稀土金属材料研究院 | Tungsten slag treatment method |
| US20130037416A1 (en) * | 2010-07-15 | 2013-02-14 | Guangxi Non-Ferrous Metals Group Huiyuanmengye Co., Ltd. | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide |
| CN103466713A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Method for preparing manganese sulfate monohydrate with low-grade manganese ore through primary crystallization by high-pressure method |
| CN104195331A (en) * | 2014-09-02 | 2014-12-10 | 湖南科技大学 | Method for preparing high-purity manganese sulfate through extracting low-grade pyrolusite by using rice straw |
| CN107447110A (en) * | 2017-07-07 | 2017-12-08 | 北京盖雅环境科技有限公司 | A kind of preparation method of LITHIUM BATTERY manganese sulfate |
| CN108711656A (en) * | 2018-08-24 | 2018-10-26 | 广西师范大学 | A kind of recoverying and utilizing method of waste and old lithium ion battery |
| CN109868373A (en) * | 2019-02-02 | 2019-06-11 | 广东芳源环保股份有限公司 | A method of substep leaching nickel, cobalt from nickel, cobalt, manganese mixture |
-
2019
- 2019-07-02 CN CN201910587886.7A patent/CN110127766A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002717A (en) * | 1975-01-09 | 1977-01-11 | Deepsea Ventures, Inc. | Refining of manganese oxide ores |
| CN1311340A (en) * | 2000-02-28 | 2001-09-05 | 邓建成 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
| CN101337692A (en) * | 2008-08-21 | 2009-01-07 | 广西远辰锰业有限公司 | Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material |
| US20130037416A1 (en) * | 2010-07-15 | 2013-02-14 | Guangxi Non-Ferrous Metals Group Huiyuanmengye Co., Ltd. | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide |
| CN102212697A (en) * | 2011-05-18 | 2011-10-12 | 湖南稀土金属材料研究院 | Tungsten slag treatment method |
| CN102212697B (en) * | 2011-05-18 | 2013-07-10 | 湖南稀土金属材料研究院 | Tungsten slag treatment method |
| CN103466713A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Method for preparing manganese sulfate monohydrate with low-grade manganese ore through primary crystallization by high-pressure method |
| CN104195331A (en) * | 2014-09-02 | 2014-12-10 | 湖南科技大学 | Method for preparing high-purity manganese sulfate through extracting low-grade pyrolusite by using rice straw |
| CN107447110A (en) * | 2017-07-07 | 2017-12-08 | 北京盖雅环境科技有限公司 | A kind of preparation method of LITHIUM BATTERY manganese sulfate |
| CN108711656A (en) * | 2018-08-24 | 2018-10-26 | 广西师范大学 | A kind of recoverying and utilizing method of waste and old lithium ion battery |
| CN109868373A (en) * | 2019-02-02 | 2019-06-11 | 广东芳源环保股份有限公司 | A method of substep leaching nickel, cobalt from nickel, cobalt, manganese mixture |
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