CN109336184B - Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate - Google Patents
Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate Download PDFInfo
- Publication number
- CN109336184B CN109336184B CN201811286919.6A CN201811286919A CN109336184B CN 109336184 B CN109336184 B CN 109336184B CN 201811286919 A CN201811286919 A CN 201811286919A CN 109336184 B CN109336184 B CN 109336184B
- Authority
- CN
- China
- Prior art keywords
- manganese sulfate
- kiln
- equal
- stage
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 38
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 37
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 37
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000704 physical effect Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000005086 pumping Methods 0.000 claims abstract description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000003345 natural gas Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 235000006748 manganese carbonate Nutrition 0.000 description 3
- 239000011656 manganese carbonate Substances 0.000 description 3
- 229940093474 manganese carbonate Drugs 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/52—Preparation of sulfur dioxide by roasting sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for utilizingThe two-stage dry manganese sulfate roasting process of preparing manganous-manganic oxide includes the following steps: maintaining the temperature at 500-600 deg.C for 2hr to dry the materials, and pumping the water vapor in the kiln into a washing tower by a draught fan to wash in the drying process; calcining the dried material at 1150-1350 deg.C for 6hr to obtain SO2Introducing gas into a sulfur dioxide collection system by using an induced draft fan; conveying the calcined material to a cooling section, and cooling to normal temperature; finally, the manganous-manganic oxide is prepared by crushing. The manganous-manganic oxide prepared by the invention has the main content of more than or equal to 71.00 percent by mass based on Mn, and has the advantages of high purity, less impurities, and the indexes of tap density, apparent density and the like which can well meet the physical property requirements of the lithium manganate precursor for the new energy battery. In addition, the tail gas is utilized, so that the environmental influence is reduced, and the comprehensive utilization rate of raw materials is improved.
Description
Technical Field
The invention relates to the technical field of production of lithium manganate precursors for new energy batteries, and particularly relates to a method for preparing manganous-manganic oxide by two-stage dry roasting of manganese sulfate.
Background
The development of new energy automobiles greatly promotes the development of the lithium battery industry, and in the lithium battery industry, particularly, a lithium manganate battery is high in capacitance, high in charging frequency, safe to use, easy to recover and popular with users and researchers, and the precursor of the battery, namely trimanganese tetroxide, which is wide in market has obvious price advantage compared with materials of nickel, cobalt and other elements, so that the industrial preparation technology of the trimanganese tetroxide is rapidly developed.
At present, the industrial preparation technology of manganous-manganic oxide is classified according to the existence of a solvent in the generation process: firstly, a wet production technology; secondly, dry production technology.
The wet production technology comprises a metal manganese (electrolytic manganese) powder aqueous solution oxidation method; adding ammonia water or ammonium bicarbonate into manganese sulfate solution, and then adding oxidant to carry out oxidation. The former method has high energy consumption and high price, and other impurities are brought in the production process to influence the purity of the trimanganese tetroxide, so that the product use is limited; the latter has more chemical units, complex production route and greater difficulty in process control; and a large amount of waste water is generated in the production processes of the two, which brings great difficulty to environmental protection treatment.
The dry production technology has two types, namely, a manganese carbonate or manganese hydroxide direct roasting method, and the method has a mature process route and is a means for mainly producing the manganese tetraoxide at present. Manganese carbonate is generally produced by carbonizing manganese sulfate, manganese hydroxide is produced by neutralizing manganese sulfate with alkali, and both manganese carbonate and manganese hydroxide need co-production of manganese sulfate, so that the production cost is increased. Secondly, a Two-stage Manganese Sulfate roasting method (TCM for short) has been studied and explored by many researchers and entrepreneurs for a period of time in the past, but has some problems, such as the prepared product is far away from the physical property requirement of the lithium manganate precursor for the new energy battery, the impurity content is high, the roasting atmosphere and means are not clear, the adopted production process has serious environmental pollution, the production process has great difficulty, the safety risk is high, and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method for preparing trimanganese tetroxide by using two-stage dry roasting of manganese sulfate.
The chemical reaction principle of the invention is as follows:
first stage calcination:
MnSO4.H20＝MnSO4+H20
and (3) second-stage calcination:
(1)MnSO4＝MnO+SO3
(2)6MnO+O2＝2Mn3O4
(3)2SO3＝2SO2+O2
comprehensive reaction: 3MnSO4＝Mn3O4+3SO2+O2
During the reaction, the valence of manganese is increased, and Mn+2→Mn+3Valence of oxygen is increased, O-2→ O0, the valence of sulfur lowers by S+6→S+4It is a disproportionation reaction.
The specific technical scheme of the invention is as follows: a preparation method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate comprises the following steps:
A. selection of raw materials: preferably selecting a manganese sulfate monohydrate raw material meeting the quality requirement of a new energy lithium battery precursor product, wherein the quality requirement of the manganese sulfate raw material is as follows: the mass percentage of the main content is more than or equal to 32.2 percent in terms of Mn;
B. first stage calcination: conveying the raw materials into a first section of drying kiln, heating the drying kiln to 500-600 ℃, drying the materials, keeping the materials in the kiln for 2hr, and pumping water vapor in the kiln into a washing tower by using an induced draft fan to wash the materials in the drying process, wherein the water vapor is discharged after reaching the standard;
C. and (3) second-stage calcination: conveying the material dried in the step B to a second-stage roasting kiln, heating to 1150-1350 ℃ for roasting for 6hr, and producing SO2Introducing gas into an industrial sulfuric acid production system or a liquefied sulfur dioxide system by using an induced draft fan;
D. and (3) cooling: c, conveying the calcined material in the step C to a cooling section, and cooling to normal temperature;
E. crushing: and D, conveying the material cooled in the step D to a jet mill set for crushing to obtain a lithium manganate precursor-manganous oxide for the new energy battery.
Further, step B and step C are performed in a rotary kiln.
Further, step B and step C are performed in a roller kiln.
Further, the heat source used for the calcination in the steps B and C is natural gas.
And furthermore, the kiln interior calcining atmosphere of the second-stage calcining kiln in the step C is connected with the atmosphere.
Further, the cooling in step D is performed by externally circulating cooling water in a sealed state.
Further, the cooling in step D is performed by using a shielding gas.
Compared with the prior art, the invention has the following beneficial effects:
1. in the first stage of calcination procedure, the water vapor in the kiln is pumped into the washing tower by the induced draft fan to wash the tail gas, and then the tail gas is discharged after reaching the standard, so that the moisture is prevented from being brought into the second stage of calcination procedure, and the second stage of calcination procedure can generate sulfur dioxide, and if the moisture is brought into the second stage of calcination procedure, the equipment can be corroded.
2. In the second stage of the calcining process, the sulfur dioxide gas decomposed by the manganese sulfate is introduced into an industrial sulfuric acid production system or a liquefied sulfur dioxide system by using an induced draft fan, the calcining atmosphere in the kiln is connected with the atmosphere, and an adjustable ventilation device is arranged, so that the organized recovery of the sulfur dioxide gas and air decomposed in the kiln is ensured, and meanwhile, the percentage content index of the sulfur dioxide gas in the mixed gas is ensured to meet the requirement of a sulfuric acid production device. Therefore, the tail gas can be used for preparing industrial sulfuric acid or liquid sulfur dioxide, so that the environmental influence is reduced, and the comprehensive utilization rate of raw materials is improved.
3. The manganous-manganic oxide prepared by the technology has the main content of more than or equal to 71.00 percent by mass based on Mn, and has the advantages of high purity, less impurities, and good performance meeting the physical property requirements of the lithium manganate precursor for the new energy battery in terms of indexes such as tap density, apparent density and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first embodiment is as follows:
selecting materials:
the quality requirement of the raw material manganese sulfate is as follows: the mass percentage of the main content is more than or equal to 32.2 percent in terms of Mn.
The mass percentage content index of impurities in the raw material manganese sulfate is shown in the table I.
Table one: impurity mass percentage content index in raw material manganese sulfate
First stage calcination: conveying 500kg of manganese sulfate raw material meeting the requirement to a drying bin by using a belt conveyor or vacuum airflow, uniformly feeding the manganese sulfate raw material into a first-stage drying kiln by adopting spiral control feeding (the frequency conversion is 10Hz), controlling the speed of the rotary kiln to be 35 s/circle, heating the drying kiln by using natural gas to enable the temperature of the drying kiln to reach 600 ℃, drying the material, and maintaining the retention time of the material in the kiln to be 2 hours. And pumping the water vapor in the kiln into a washing tower by using an induced draft fan to wash the tail gas, and discharging the tail gas after reaching the standard.
And (3) second-stage calcination: detecting the material dried in the kiln to water content of 0.001%, directly conveying to a transfer bin, uniformly feeding into a second-stage roasting kiln by adopting spiral control feeding (frequency conversion is 7Hz), controlling the speed of the rotary kiln to be 55 s/circle, heating the temperature in the roasting kiln to 1150 ℃ by using natural gas, calcining the dried manganese sulfate, controlling the constant temperature to 1150 ℃ and calcining for 6hr, wherein the SO generated by calcination2The gas is introduced into an industrial sulfuric acid production system or a liquefied sulfur dioxide system by using an induced draft fan.
And (3) cooling: the calcined material is directly conveyed to a cooling machine for closed cooling, and circulating water is adopted for cooling outside the cylinder body.
Crushing: and (3) conveying the cooled material to an airflow pulverizer set for pulverizing, and bagging by using an automatic bagging system to finally obtain 225.00kg of product, wherein the main content of manganese is 71.69% through detection, and the other indexes are shown in the second table and the third table.
Table two: product Mn3O4Mass percentage content index of medium impurities
Table three: product Mn3O4Physical property index
| Physical Properties | D50(nm) | BET(m2/g) | Apparent density g/cm3 | Tap density g/cm3 | XRD |
| Index (I) | 12 | 1.0 | 1.3 | 2.2 | Without impurity phase |
The above data indicate that the product calcined through the rotary kiln is a satisfactory product.
Example two:
selecting materials:
the quality requirement of the raw material manganese sulfate is as follows: the mass percentage of the main content is more than or equal to 32.2 percent in terms of Mn.
The index table I shows the mass percentage content of impurities in the raw material manganese sulfate.
First stage calcination: conveying 500kg of manganese sulfate raw material meeting the requirement to a drying bin by using a belt conveyor or vacuum airflow, uniformly feeding the manganese sulfate raw material into a first section of drying kiln by adopting spiral control feeding (the frequency conversion is 10Hz), controlling the speed of the rotary kiln to be 35 s/circle, heating the drying kiln by using natural gas to ensure that the temperature of the drying kiln reaches 550 ℃, drying the material, and maintaining the retention time of the material in the kiln to be 2 hours. And pumping the water vapor in the kiln into a washing tower by using an induced draft fan to wash the tail gas, and discharging the tail gas after reaching the standard.
And (3) second-stage calcination: detecting the material dried in the kiln to water content of 0.001%, directly conveying to a transfer bin, uniformly feeding into a second-stage roasting kiln by adopting spiral control feeding (frequency conversion of 7Hz), controlling the speed of the rotary kiln to 55 s/circle, heating the temperature in the roasting kiln to 1250 ℃ by using natural gas, calcining the dried manganese sulfate, controlling the constant temperature to 1250 ℃ for 6hr, and calcining the generated SO2Air inducing machine for gasThe industrial sulfuric acid production system or the liquefied sulfur dioxide system.
And (3) cooling: the calcined material is directly conveyed to a cooling machine for closed cooling, and circulating water is adopted for cooling outside the cylinder body.
Crushing: and (3) conveying the cooled material to an airflow pulverizer set for pulverization, and bagging by using an automatic bagging system to finally obtain 228.00kg of product, wherein the main content of manganese is 71.46% through detection, and the other indexes are shown in the fourth table and the fifth table.
Table four: product Mn3O4Mass percentage content index of medium impurities
Table five: product Mn3O4Physical property index
| Physical Properties | D50(nm) | BET(m2/g) | Apparent density g/cm3 | Tap density g/cm3 | XRD |
| Index (I) | 11 | 1.0 | 1.4 | 2.23 | Without impurity phase |
The above data indicate that the product calcined through the rotary kiln is a satisfactory product.
Example three:
selecting materials:
the quality requirement of the raw material manganese sulfate is as follows: the mass percentage of the main content is more than or equal to 32.2 percent in terms of Mn.
The mass percentage content index of impurities in the raw material manganese sulfate is shown in the table I.
Two-stage calcination: conveying 800kg of manganese sulfate raw material meeting the requirements to a raw material transfer bin by using a belt conveyor or vacuum airflow for automatic feeding; the whole roller kiln system is operated, auxiliary equipment is operated simultaneously, the temperature of the drying section and the calcining section of the roller kiln is increased, when the temperature meets the process control requirements (namely drying is carried out at 600 ℃ and calcining is carried out at 1350 ℃), a feeding manipulator is started to feed materials to the production line from a transfer bin, and the loading weight of each sagger is controlled to be 6 kg; when the materials pass through the drying section, drying all the moisture of the materials, and detecting the moisture content in the materials to be 0.005%; the water vapor is pumped into a gas washing and discharging system by a fan for treatment, the material continues to run to a calcining section, and SO is decomposed from manganese sulfate2The gas is pumped to an industrial sulfuric acid production system by a fan or liquefied SO2Provided is a system.
And (3) cooling: mn formed by decomposition3O4And continuously running to a cooling section of the roller kiln, and cooling by adopting nitrogen protective gas.
Crushing: and (3) moving the cooled material to an external line track, pouring the material into a transfer bin by using a manipulator, putting the empty sagger back to the track, crushing the material by using an airflow crushing device to produce a product meeting the requirement, and packaging by using an automatic packaging system to finally obtain 359.50kg of the product, wherein the main content of manganese is 71.28% by detection, and the other indexes are shown in a sixth table and a seventh table.
Table six: product Mn3O4Mass percent of medium impurityIndex of fractional content
TABLE VII: product Mn3O4Physical property index
| Physical Properties | D50(nm) | BET(m2/g) | Apparent density g/cm3 | Tap density g/cm3 | XRD |
| Index (I) | 11.0 | 0.95 | 1.5 | 2.45 | Without impurity phase |
The above shows that the product calcined by the roller kiln is also a satisfactory product.
Claims (8)
1. A preparation method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate comprises the following steps:
A. selection of raw materials: the manganese sulfate monohydrate raw material meets the quality requirements of new energy lithium battery precursor products, and the quality requirements of the raw material manganese sulfate are as follows: the main content is more than or equal to 32.2 percent in terms of Mn, and the indexes of the impurities in the raw material manganese sulfate in percentage by mass are as follows: si is less than or equal to 0.01, Fe is less than or equal to 0.005, K is less than or equal to 0.005, Na is less than or equal to 0.005, Co is less than or equal to 0.01, Zn is less than or equal to 0.01, Cu is less than or equal to 0.001, Mg is less than or equal to 0.02, Ni is less than or equal to 0.01, and Pb is less than or equal to 0.002;
B. first stage calcination: conveying the raw materials into a first-stage drying kiln, heating the drying kiln to 500-600 ℃, drying the materials, maintaining the materials to stay in the kiln for 2hr, and pumping water vapor in the kiln into a washing tower by using an induced draft fan to wash the materials in the drying process, wherein the water vapor is discharged after reaching the standard, and the water content is 0.001%;
C. and (3) second-stage calcination: conveying the material dried in the step B into a second-stage roasting kiln, wherein the in-kiln roasting atmosphere of the roasting kiln is connected with the atmosphere; heating to 1150-1350 ℃ for calcination for 6hr to obtain SO2Introducing gas into a sulfur dioxide collection system by using an induced draft fan;
D. and (3) cooling: c, conveying the calcined material in the step C to a cooling section, and cooling to normal temperature;
E. crushing: and D, conveying the material cooled in the step D to a jet mill set for crushing to obtain a lithium manganate precursor, namely trimanganese tetroxide for the new energy battery, wherein the main content of manganese is 71.46%, and the impurity mass percentage content index of the prepared trimanganese tetroxide is as follows: si 0.009, Fe 0.008, K0.007, Na 0.035, Co 0.003, Ca 0.028, Mg 0.02, Ni 0.008, Pb 0.0015, H2O0.35, and the physical property indexes are as follows: d5011 nm, BET 1.0 m2(g), apparent density 1.4 g/cm3Tap density of 2.23 g/cm3XRD has no impurity phase.
2. The method for preparing trimanganese tetroxide by using manganese sulfate two-stage dry roasting as claimed in claim 1, wherein steps B and C are performed in a rotary kiln.
3. The method for preparing trimanganese tetroxide by using the two-stage dry roasting of manganese sulfate as claimed in claim 1, wherein the steps B and C are performed in a roller kiln.
4. The method for preparing manganous-manganic oxide by using two-stage dry roasting of manganese sulfate as claimed in claim 1, wherein a heat source used for calcining in the steps B and C is natural gas.
5. The method for preparing manganous-manganic oxide by using two-stage dry roasting of manganese sulfate as claimed in claim 1, wherein the cooling in the step D is performed by externally circulating cooling water in a sealed state.
6. The method for preparing manganous-manganic oxide by using two-stage dry roasting of manganese sulfate as claimed in claim 1, wherein the cooling in step D is cooling by using protective gas.
7. The method for preparing manganous-manganic oxide by using two-stage dry roasting of manganese sulfate as claimed in claim 1, wherein the sulfur dioxide collection system in the step C is an industrial sulfuric acid production system.
8. The method for preparing manganous-manganic oxide by using two-stage dry roasting of manganese sulfate as claimed in claim 1, wherein the sulfur dioxide collection system in the step C is a liquefied sulfur dioxide system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811286919.6A CN109336184B (en) | 2018-10-31 | 2018-10-31 | Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811286919.6A CN109336184B (en) | 2018-10-31 | 2018-10-31 | Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109336184A CN109336184A (en) | 2019-02-15 |
| CN109336184B true CN109336184B (en) | 2021-01-19 |
Family
ID=65313237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811286919.6A Active CN109336184B (en) | 2018-10-31 | 2018-10-31 | Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109336184B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825106A (en) * | 2020-03-16 | 2020-10-27 | 宁夏天元锰业集团有限公司 | Two-stage calcination treatment method for electrolytic manganese metal ammonium sulfate slag |
| CN112079392A (en) * | 2020-09-22 | 2020-12-15 | 李家红 | Preparation method of lithium ion battery anode material |
| CN112299492A (en) * | 2020-10-30 | 2021-02-02 | 湖南德景源科技有限公司 | Preparation method of battery-grade cobaltosic oxide |
| CN112357964A (en) * | 2020-10-30 | 2021-02-12 | 杜长福 | Preparation method of battery-grade trimanganese tetroxide |
| CN112795985A (en) * | 2020-12-29 | 2021-05-14 | 无锡晶石新型能源股份有限公司 | Preparation method of doped single crystal manganous-manganic oxide |
| CN112897583B (en) * | 2021-04-27 | 2023-11-07 | 胡莉 | Battery grade monocrystal manganous manganic oxide preparation device and method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163414C (en) * | 1999-09-30 | 2004-08-25 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
| CN1927727A (en) * | 2006-09-21 | 2007-03-14 | 广西大学 | Method of preparing high-purity manganomanganic oxide by pyrolyzing manganese sulfate at high temperature |
| CN102633306B (en) * | 2012-04-10 | 2014-01-22 | 四川大学 | Preparation method of high-purity trimanganese tetroxide |
| CN105948130B (en) * | 2016-07-05 | 2017-06-09 | 湖南蒙达新能源材料有限公司 | A kind of mangano-manganic oxide, preparation method and applications |
| CN108069459B (en) * | 2017-12-14 | 2019-07-16 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 mangano-manganic oxide and its industrial production process |
-
2018
- 2018-10-31 CN CN201811286919.6A patent/CN109336184B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109336184A (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109336184B (en) | Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate | |
| US10122052B2 (en) | Systems and methods for purifying and recycling lead from spent lead-acid batteries | |
| AU733390B2 (en) | Method of preparing li1+xmn2-xo4 for use as secondary battery electrode | |
| CN104201378B (en) | Method for preparing high-nickel ternary cathode material of lithium ion battery | |
| CN107851794B (en) | Method for producing positive electrode active material for lithium secondary battery | |
| US5874058A (en) | Method of preparing Li1+x MN2-x O4 for use as secondary battery electrode | |
| CN108933308B (en) | Comprehensive recycling method for anode and cathode of scrapped lithium battery | |
| CN109742380B (en) | Preparation method of lithium-rich manganese-based positive electrode material | |
| CN107792891A (en) | A kind of method and application that cobalt-nickel-manganese oxide compound is produced with nickel cobalt manganese elemental metals | |
| CN114014294B (en) | Method for preparing lithium iron phosphate by using pyrite and lithium iron phosphate material | |
| CN107857244A (en) | A kind of recycling treatment process of LiFePO4 waste material | |
| JP4345934B2 (en) | Low temperature lithiation of hydroxides containing cobalt, nickel and manganese using a wet process | |
| CN115020659A (en) | LiFePO 4 Preparation method of/C composite positive electrode material | |
| CN112079392A (en) | Preparation method of lithium ion battery anode material | |
| CN111924892A (en) | Method for selectively recovering lithium ion battery electrode powder | |
| CN110436429A (en) | A kind of method that thermal decomposition method prepares battery-grade iron phosphate | |
| CN116230842B (en) | Preparation method of lithium supplementing agent | |
| CN111268747B (en) | Recycling method and system of waste ternary battery positive electrode material based on hydrochloric acid regeneration cycle | |
| KR100550373B1 (en) | Manufacturing method of Li1 + xMn2-xO4 for use as a secondary battery electrode | |
| EP0931022A1 (en) | METHOD OF PREPARING Li 1+x?Mn 2-x?O 4? FOR USE AS SECONDARY BATTERY ELECTRODE | |
| KR100477400B1 (en) | Method for manufacturing Lil + xMn2-xO4 for secondary battery electrode | |
| CN116425203A (en) | Preparation method of high-purity manganese new energy material | |
| CN117367118A (en) | Efficient and energy-saving spodumene roasting transformation system and method | |
| JP2021109811A (en) | Method for firing nickel hydroxide particles, and method for producing nickel oxide fine powder using the same | |
| CN116101993A (en) | Preparation method of iron phosphate and lithium iron phosphate prepared by adopting method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190306 Address after: 621000 Dianhui International, South Section of Hengyuan Avenue, Anzhou District, Mianyang City, Sichuan Province Applicant after: Hu Yihua Address before: 622656 Dianhui International, South Section of Hengyuan Avenue, Anzhou District, Mianyang City, Sichuan Province Applicant before: Hu Yihua Applicant before: Wang Zhengwei |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Hu Yihua Inventor before: Hu Yihua Inventor before: Wang Zhengwei |
|
| CB03 | Change of inventor or designer information | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220124 Address after: 628100 No. 1, Yongxing Road, Zhuangzi Industrial Park, Zhuyuan Town, Qingchuan County, Guangyuan City, Sichuan Province Patentee after: Sichuan Qingyuan New Material Co.,Ltd. Address before: 621000 Dianhui International, South Section of Hengyuan Avenue, Anzhou District, Mianyang City, Sichuan Province Patentee before: Hu Yihua |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220624 Address after: 628100 No.1 Binjiang Road, Zhuyuan Town, Qingchuan County, Guangyuan City, Sichuan Province (No.56, first floor, Qingchuan Economic Development Zone Management Committee) Patentee after: Sichuan Xingheng Qingyuan New Material Technology Co.,Ltd. Address before: 628100 No. 1, Yongxing Road, Zhuangzi Industrial Park, Zhuyuan Town, Qingchuan County, Guangyuan City, Sichuan Province Patentee before: Sichuan Qingyuan New Material Co.,Ltd. |
|
| TR01 | Transfer of patent right |