CN116462231A - Battery-grade manganese sulfate production device and method - Google Patents
Battery-grade manganese sulfate production device and method Download PDFInfo
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- CN116462231A CN116462231A CN202310383348.2A CN202310383348A CN116462231A CN 116462231 A CN116462231 A CN 116462231A CN 202310383348 A CN202310383348 A CN 202310383348A CN 116462231 A CN116462231 A CN 116462231A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 41
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 41
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- 238000002425 crystallisation Methods 0.000 claims abstract description 89
- 230000008025 crystallization Effects 0.000 claims abstract description 89
- 239000002562 thickening agent Substances 0.000 claims abstract description 58
- 238000000967 suction filtration Methods 0.000 claims abstract description 53
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000012452 mother liquor Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000003825 pressing Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 29
- 239000000706 filtrate Substances 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 4
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 230000008020 evaporation Effects 0.000 description 7
- 239000010413 mother solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a device and a method for producing battery-grade manganese sulfate, comprising a plurality of reaction kettles, a filter pressing kettle, an air compressor, a plurality of buffer tanks, a plurality of suction filtration kettles, a preheater, a plurality of forced circulation evaporators, a plurality of crystallizers, a plurality of vapor compressors, a plurality of thickeners, a plurality of centrifuges, a mixing tank, a first mother liquid tank and a second mother liquid tank; the forced circulation evaporators, the crystallizers, the vapor compressors, the thickeners, the centrifuges and the mixing tanks respectively form a primary crystallization system and a secondary crystallization system. The method uses the mother liquor circulation and multistage high-pressure crystallization modes to purify the manganese sulfate monohydrate, has less waste liquid discharge amount, and simultaneously recovers a large amount of water resources; the process has wide application range, and can be applied to the production and purification processes of manganese sulfate solutions with different impurity contents; the invention has simple process, low equipment investment and easy realization of industrialization.
Description
Technical Field
The invention relates to the technical field of manganese sulfate production, in particular to a device and a method for producing battery-grade manganese sulfate.
Background
The battery-grade manganese sulfate is a ternary positive electrode material and a main synthetic salt of a lithium manganate positive electrode material, the battery-grade high-purity manganese sulfate monohydrate has severe requirements on impurities, and potassium, sodium, calcium, magnesium, heavy metal ions and the like which have great influence on a lithium ion battery must be strictly controlled.
Through searching, the Chinese patent with the application number of CN114772648A discloses a method for purifying and producing battery-grade manganese sulfate by using industrial-grade manganese sulfate, which aims to research a low-cost and stable-quality green battery-grade manganese sulfate production process, mainly aims at industrial-grade manganese sulfate and is improved in the production flow, and a process combination device is not considered to be designed together.
At present, most of domestic manganese sulfate production processes still have the problems of high impurity removal cost, low manganese sulfate purity, complex process, narrow application range and the like, and based on the problems, the invention provides a method and a device for producing battery-grade manganese sulfate monohydrate, which are suitable for industrialization.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a device and a method for producing battery-grade manganese sulfate.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the battery-level manganese sulfate production device comprises a plurality of reaction kettles, a filter pressing kettle, an air compressor, a plurality of buffer tanks, a plurality of suction filtration kettles, a preheater, a plurality of forced circulation evaporators, a plurality of crystallizers, a plurality of vapor pressure compressors, a plurality of thickeners, a plurality of centrifuges, a mixing tank, a first mother liquid tank and a second mother liquid tank;
the device comprises a first mother tank, a second mother tank, a forced circulation evaporator, a crystallizer, a vapor pressure compressor, a thickener, a centrifuge and a mixing tank, wherein the forced circulation evaporator, the crystallizer, the vapor pressure compressor, the thickener, the centrifuge and the mixing tank respectively form a primary crystallization system and a secondary crystallization system, the primary crystallization system is connected with the first mother tank, and the secondary crystallization system is connected with the second mother tank.
Further, the reaction kettles comprise a first reaction kettle, a second reaction kettle, a third reaction kettle, a fourth reaction kettle, a fifth reaction kettle and a sixth reaction kettle;
the buffer tank comprises a first buffer tank, a second buffer tank and a third buffer tank;
further, the number of the suction filtration kettles is at least two, a plurality of the suction filtration kettles are connected in parallel, the suction filtration kettles comprise a first suction filtration kettle and a second suction filtration kettle, and a pretreatment vacuum system is arranged between the first suction filtration kettle and the second suction filtration kettle;
the filter pressing kettles are connected with an air compressor, and a plurality of filter pressing kettles are connected in parallel;
the first suction filtration kettle and the second suction filtration kettle are both connected with a pretreatment vacuum system, and the first suction filtration kettle and the second suction filtration kettle are used in parallel;
the thickener is at least connected with three jackets in parallel for intermittent use, the thickener is provided with a jacket for heat preservation, and the thickener is connected with high-temperature high-pressure steam for pressure maintaining;
further, the first reaction kettle and the second reaction kettle are both connected with the first buffer tank through a filter pressing kettle;
the first buffer tank is connected with the first pump through a third reaction kettle and a fourth reaction kettle respectively;
the second buffer tank is connected with a second suction filtration kettle through a fourth reaction kettle and a fifth reaction kettle respectively, and the second suction filtration kettle is connected with a third buffer tank;
the third buffer tank is connected with the preheater, the preheater is connected with the first mother liquor tank through the first crystallization system, and the preheater is connected with the second crystallization system and the second mother liquor tank through the mixing tank.
According to another aspect of the invention, a method based on the battery-grade manganese sulfate production device is also provided.
The production method of the battery-grade manganese sulfate comprises the following steps:
s1: feeding the acid leaching manganese sulfate solution into a first or a second reaction kettle, adding ferric sulfate, keeping the first and the second reaction kettles at a temperature by saturated steam, feeding the solid-liquid phase of the reaction kettle into a filter pressing kettle for filtering after the reaction is finished, filtering out filter residues, and feeding the filtrate into a first buffer tank;
s2: the filtrate in the first buffer tank is sent to a third reaction kettle or a fourth reaction kettle, hydrogen peroxide and manganese hydroxide powder are added, the PH value of the solution is regulated to 5.0, the reaction time is 1h, the solution enters the first suction filtration kettle for filtration after the reaction is finished, filter residues are filtered out, and the filtrate is sent to the second buffer tank;
s3: the filtrate in the second buffer tank is sent to a fourth or fifth reaction kettle, manganese fluoride is added, the fourth reaction kettle and the fifth reaction kettle are insulated by saturated steam, the filtrate enters a second suction filtration kettle for filtration after the reaction is finished, filter residues are filtered out, and the filtrate is sent to a third buffer tank;
s4: the material enters a preheater from a third buffer tank to be preheated to 95-98 ℃, and the preheated material enters a primary crystallization process;
s5: after primary crystallization is completed, the liquid phase is sent into a first mother liquid tank after solid-liquid separation of a first centrifugal machine, wet salt output by the first centrifugal machine is directly dissolved in a mixing tank, the dissolution liquid is continuously subjected to secondary crystallization, mother liquid after solid-liquid separation of a second centrifugal machine is sent into a second mother liquid tank, materials in the second mother liquid tank are sent into the mixing tank, and then the wet salt output by the second centrifugal machine is dried and packaged to obtain the battery-grade manganese sulfate monohydrate product.
Further, the PH value of the reaction of the first reaction kettle and the second reaction kettle is 2.0-3.0, the reaction time is 2-3h, and the reaction temperature is 85-90 ℃;
the third and fourth reaction kettles adjust the PH value of the solution to 5.0, and the reaction time is 1h;
the pH value of the solution in the fifth reaction kettle and the solution in the sixth reaction kettle are 4.0-5.0, the reaction time is 2-3h, and the reaction temperature is 60-65 ℃.
Further, a primary crystallization system and a secondary crystallization system are used for the primary crystallization process and the secondary crystallization process, respectively, wherein:
the crystallization process of the primary crystallization system and the crystallization process of the secondary crystallization system are operated identically, and specifically: the crystallization temperature is 160-180 ℃, the pressure of the evaporating chamber is 0.6-1.0Mpa, and the pressure of the steam which is connected into the thickener is 1.0-1.2Mpa.
Further, the high-temperature condensed water in the primary crystallization process preheats materials to 98 ℃ in a preheater, and the high-temperature condensed water in the secondary crystallization process dissolves primary crystallization wet salt in a mixing tank.
Further, the vapor compressors are centrifugally compressed, and when a plurality of vapor compressors are connected, the vapor compressors are connected in series, and the forced circulation evaporators in the primary crystallization system and the secondary crystallization system are used for providing heat sources.
Compared with the prior art, the invention has the beneficial effects that:
the method uses the mother liquor circulation and multistage high-pressure crystallization modes to purify the manganese sulfate monohydrate, has less waste liquid discharge amount, and simultaneously recovers a large amount of water resources;
the process has wide application range, and can be applied to the production and purification processes of manganese sulfate solutions with different impurity contents;
the invention has simple process, low equipment investment and easy realization of industrialization.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
FIG. 1 is a schematic diagram of a battery-grade manganese sulfate production device and a production flow in an embodiment of the invention;
FIG. 2 is a flow chart of a secondary crystallization system according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
According to an embodiment of the invention, a battery-grade manganese sulfate production device is provided.
Referring to fig. 1-2, a battery-grade manganese sulfate production device comprises a plurality of reaction kettles, a filter pressing kettle, an air compressor, a plurality of buffer tanks, a plurality of suction filtration kettles, a preheater, a plurality of forced circulation evaporators, a plurality of crystallizers, a plurality of vapor compressors, a plurality of thickeners, a plurality of centrifuges, a mixing tank, a first mother liquid tank and a second mother liquid tank;
the device comprises a first mother tank, a second mother tank, a forced circulation evaporator, a crystallizer, a vapor pressure compressor, a thickener, a centrifuge and a mixing tank, wherein the forced circulation evaporator, the crystallizer, the vapor pressure compressor, the thickener, the centrifuge and the mixing tank respectively form a primary crystallization system and a secondary crystallization system, the primary crystallization system is connected with the first mother tank, and the secondary crystallization system is connected with the second mother tank.
In a specific embodiment of the present application, the reaction kettles include a first reaction kettle, a second reaction kettle, a third reaction kettle, a fourth reaction kettle, a fifth reaction kettle, and a sixth reaction kettle;
the buffer tank comprises a first buffer tank, a second buffer tank and a third buffer tank;
the number of the suction filtration kettles is at least two, a plurality of the suction filtration kettles are connected in parallel, the suction filtration kettles comprise a first suction filtration kettle and a second suction filtration kettle, and a pretreatment vacuum system is arranged between the first suction filtration kettle and the second suction filtration kettle;
the filter pressing kettles are connected with an air compressor, and a plurality of filter pressing kettles are connected in parallel;
the first suction filtration kettle and the second suction filtration kettle are both connected with a pretreatment vacuum system, and the first suction filtration kettle and the second suction filtration kettle are used in parallel;
the thickener is at least connected with three thickeners in parallel for intermittent use, the thickener is provided with a jacket for heat preservation, and the thickener is connected with high-temperature high-pressure steam for pressure maintaining.
In the embodiment, the pH value of the first reaction kettle and the second reaction kettle is 2.0-3.0, the reaction time is 2-3h, and the reaction temperature is 85-90 ℃;
the third and fourth reaction kettles adjust the PH value of the solution to 5.0, and the reaction time is 1h;
the pH value of the solution in the fifth reaction kettle and the solution in the sixth reaction kettle are 4.0-5.0, the reaction time is 2-3h, and the reaction temperature is 60-65 ℃.
In the specific embodiment of the application, on the basis of the scheme, the first reaction kettle and the second reaction kettle are connected with the first buffer tank through a filter pressing kettle;
the first buffer tank is connected with the first pump through a third reaction kettle and a fourth reaction kettle respectively;
the second buffer tank is connected with a second suction filtration kettle through a fourth reaction kettle and a fifth reaction kettle respectively, and the second suction filtration kettle is connected with a third buffer tank;
the third buffer tank is connected with the preheater, the preheater is connected with the first mother liquor tank through the first crystallization system, and the preheater is connected with the second crystallization system and the second mother liquor tank through the mixing tank.
In a specific embodiment of the present application, the primary crystallization system: the device is formed by sequentially connecting the first-stage forced circulation evaporator, the second-stage forced circulation evaporator, the first-stage crystallizer, the second-stage crystallizer, a first thickener, a second thickener, a third thickener and the first centrifuge;
and (3) a secondary crystallization system: the three-stage forced circulation evaporator, the four-stage forced circulation evaporator, the three-stage crystallizer, the four-stage crystallizer, the fourth thickener, the fifth thickener, the sixth thickener and the second centrifuge are sequentially connected.
In a specific embodiment of the present application, the vapor compressors are centrifugal compressors, and a plurality of the vapor compressors are connected in series, so that the vapor compressors are used for providing heat sources for the forced circulation evaporators in the primary crystallization system and the secondary crystallization system.
According to another embodiment of the present invention, there is also provided a method according to the above battery grade manganese sulfate production device.
Example 1
Referring to fig. 1, a method for producing battery-grade manganese sulfate, according to the implementation of the present application, specifically comprises the following steps:
s1: the acid leaching manganese sulfate solution is sent to a first reaction kettle or a second reaction kettle, ferric sulfate is added, the PH value of the solution is regulated to 2.0-3.0, the reaction time is 2-3h, the reaction temperature is 85-90 ℃, the first reaction kettle and the second reaction kettle are kept warm by saturated steam, after the reaction is finished, the solid-liquid phase of the reaction kettle is sent to a filter pressing kettle for filtration, filter residues are filtered, the filtrate is sent to a first buffer tank, the filter pressing kettle is pressurized by an air compressor, the pressure medium is clean inert gas, and a plurality of filter pressing kettles can be used in parallel.
S2: the filtrate in the first buffer tank is sent to a third or fourth reaction kettle, hydrogen peroxide and manganese hydroxide powder are added, the PH value of the solution is regulated to 5.0, the reaction time is 1h, the filtrate enters a first suction filtration kettle for filtration after the reaction is finished, filter residues are filtered out, the filtrate is sent to a second buffer tank, the suction filtration kettle is connected to a vacuum system, and a plurality of suction filtration kettles can be used in parallel;
s3: and (3) sending the filtrate in the second buffer tank to a fourth or fifth reaction kettle, adding manganese fluoride, controlling the pH value of the solution to be 4.0-5.0, reacting for 2-3 hours, and keeping the temperature of the reaction at 60-65 ℃, wherein the fourth and fifth reaction kettles are kept warm by saturated steam. Filtering the mixture in a second suction filtration kettle after the reaction is finished, filtering filter residues, sending the filtrate into a third buffer tank, sending the industrial manganese sulfate solution into the third buffer tank, and connecting the suction filtration kettle to a vacuum system, wherein a plurality of suction filtration kettles can be used in parallel;
s4: the materials enter a preheater from a third buffer tank to be preheated to 95-98 ℃, and the heat source is condensed water from the primary crystallization process. The preheated material enters a primary crystallization process. The primary crystallization process is shown by a broken line in a flow chart, consists of a two-stage high-pressure evaporation crystallization process and a high-pressure thickening separation process, and means that materials preheated by a preheater are subjected to high-pressure evaporation crystallization through a primary forced circulation evaporator, a primary crystallizer, a secondary forced circulation evaporator and a secondary crystallizer in sequence, the heat sources of the primary forced circulation evaporator and the secondary forced circulation evaporator are provided by a steam compressor, and the steam compressor is a centrifugal compressor which can be used in series; the second-stage crystallizer inputs materials into a thickener, the thickener is at least connected with three intermittent use machines in parallel, the thickener is provided with a jacket for heat preservation, the thickener is connected with high-pressure steam for pressure maintaining, the thickened liquid-phase materials are returned to the first-stage forced circulation evaporator for mechanically applying, and solid phase after pressure maintaining and thickening enters a first centrifugal machine for continuous solid-liquid separation, so that a primary crystallization process is completed; in the primary crystallization process, a first-stage forced circulation evaporator, a second-stage forced circulation evaporator, a first thickener, a second thickener and a third thickener jacket (shell pass) are used for collecting high-temperature condensed water and then preheating materials in a preheater. The crystallization temperature is 160-180 ℃ and the pressure of the evaporating chamber is 0.6-1.0Mpa in the primary crystallization process, and the pressure of the steam which is connected into the thickener is 1.0-1.2Mpa;
s5: the liquid phase is sent into a first mother liquor tank after solid-liquid separation of a first centrifugal machine, the material in the first mother liquor tank returns to be mixed with the acid leaching manganese sulfate solution, a small amount of the material is discharged outwards, and the discharge capacity is not more than 20% of the mother liquor; the wet salt output from the first centrifuge is directly dissolved in the mixing tank, and the dissolution liquid is continuously subjected to a secondary crystallization process. The secondary crystallization process comprises a three-stage forced circulation evaporator, a three-stage crystallizer, a four-stage forced circulation evaporator, a four-stage crystallizer, a second vapor compressor, a fourth thickener, a fifth thickener, a sixth thickener and a second centrifuge, wherein high-temperature condensed water in the three-stage forced circulation evaporator, the fourth thickener, the fifth thickener and a sixth thickener jacket (shell side) in the secondary crystallization process is input into a mixing tank to dissolve wet salt output by the first centrifuge, and other processes are the same as the primary crystallization process; the mother solution after solid-liquid separation of the second centrifugal machine is sent to a second mother solution tank, materials in the second mother solution tank are sent to a mixing tank, a small amount of discharged materials are discharged, and the discharged materials do not exceed 20% of the mother solution. And drying and packaging wet salt output by the second centrifugal machine to obtain a battery grade manganese sulfate monohydrate product.
It is further described that the crystallization temperature in the primary crystallization process is 160-180 ℃, the pressure of the evaporating chamber is 0.6-1.0Mpa, the pressure of the steam which is connected into the thickener is 1.0-1.2Mpa, and the secondary crystallization and the primary crystallization devices are the same as the operation range;
in addition, the high-temperature condensed water in the primary crystallization process preheats materials to 98 ℃ in a preheater, and the high-temperature condensed water in the secondary crystallization process dissolves primary crystallization wet salt in a mixing tank.
Example two
And (3) inputting the acid leaching manganese sulfate solution into a first reaction kettle, adding ferric sulfate after reaching a specified liquid level, and preserving the heat of the reaction kettle by using a steam jacket at 120 ℃ for 2 hours at a reaction temperature of 90 ℃ and a reaction end point PH value of 2.0. The solid-liquid phase is input into a third reaction kettle after filter pressing, hydrogen peroxide and manganese hydroxide powder are added after reaching a specified liquid level, the reaction time is 1h, and the pH value at the reaction end point is 5.0;
after the reaction is finished, pumping filtration is carried out, filtrate is input into a fifth reaction kettle through a second buffer tank, manganese fluoride is added after reaching a specified liquid level, the reaction time is 2 hours, the reaction temperature is 60 ℃, the PH value of the reaction end point is 4.0, materials are input into a preheater through a third buffer tank, high-temperature condensed water is heated to 98 ℃, primary crystallization is carried out, the pressure of the evaporation chambers of a first-stage forced circulation evaporator and a second-stage forced circulation evaporator is 0.8Mpa, the crystallization temperature is 160 ℃, the outlet pressure of a first vapor compressor is 0.9Mpa, the discharged materials are input into a first thickener, the access pressure of the thickener is 1.0Mpa, the thickened materials are input into a first centrifuge, after centrifugal separation, mother liquor is stored in a first mother liquor tank, 20% mother liquor is discharged, 80% mother liquor is used, wet salt is dissolved in a mixing tank, the pressure of an evaporation chamber of a three-stage and four-stage forced circulation evaporator in a secondary crystallization process is 0.9Mpa, the crystallization temperature is 175 ℃, the outlet pressure of a second vapor compressor is 1.3Mpa, the access pressure of a thickener is 1.2Mpa, thickened materials are input into a first centrifugal machine, after centrifugal separation, the mother liquor is stored in the first mother liquor tank, 20% mother liquor is discharged, 80% mother liquor is used, the water content of the discharged material of a second centrifugal machine is 3%, and a battery grade manganese sulfate monohydrate product is obtained after drying and packaging.
Example III
The method comprises the steps of inputting industrial manganese sulfate solution into a third buffer tank, heating the industrial manganese sulfate solution to 98 ℃ through high-temperature condensate water, entering primary crystallization, enabling the pressure of an evaporation chamber of a primary forced circulation evaporator and the pressure of an evaporation chamber of a secondary forced circulation evaporator to be 0.78Mpa, enabling the crystallization temperature to be 170 ℃, enabling the outlet pressure of a first vapor compressor to be 1.15Mpa, inputting discharged materials into a first thickener, enabling the thickeners to be connected with the pressure of the thickeners to be 1.0Mpa, inputting thickened materials into a first centrifugal machine, storing mother liquor after centrifugal separation into a first mother liquor tank, discharging 10% of mother liquor, applying 90% of mother liquor, dissolving wet salt into a mixing tank, enabling the pressure of an evaporation chamber of the secondary forced circulation evaporator and the four-stage forced circulation evaporator to be 1.0Mpa, enabling the crystallization temperature to be 180 ℃, enabling the outlet pressure of the second vapor compressor to be 1.4Mpa, enabling the thickened materials to be connected with the pressure of the thickeners to be 1.2Mpa, inputting the thickened materials into the first centrifugal machine, storing the mother liquor into the first mother liquor tank, discharging the 10% of the mother liquor, and enabling the second centrifugal machine to be 3% of water content of the mother liquor to be stored after centrifugal separation, and obtaining a battery-grade manganese sulfate product after drying and packaging.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The battery-level manganese sulfate production device is characterized by comprising a plurality of reaction kettles, a filter pressing kettle, an air compressor, a plurality of buffer tanks, a plurality of suction filtration kettles, a preheater, a plurality of forced circulation evaporators, a plurality of crystallizers, a plurality of vapor compressors, a plurality of thickeners, a plurality of centrifuges, a mixing tank, a first mother liquid tank and a second mother liquid tank;
the device comprises a first mother tank, a second mother tank, a forced circulation evaporator, a crystallizer, a vapor pressure compressor, a thickener, a centrifuge and a mixing tank, wherein the forced circulation evaporator, the crystallizer, the vapor pressure compressor, the thickener, the centrifuge and the mixing tank respectively form a primary crystallization system and a secondary crystallization system, the primary crystallization system is connected with the first mother tank, and the secondary crystallization system is connected with the second mother tank.
2. The battery grade manganese sulfate production device according to claim 1, wherein the reaction kettles include a first reaction kettle, a second reaction kettle, a third reaction kettle, a fourth reaction kettle, a fifth reaction kettle and a sixth reaction kettle;
the buffer tank comprises a first buffer tank, a second buffer tank and a third buffer tank;
the number of the suction filtration kettles is at least two, a plurality of the suction filtration kettles are connected in parallel, the suction filtration kettles comprise a first suction filtration kettle and a second suction filtration kettle, and a pretreatment vacuum system is arranged between the first suction filtration kettle and the second suction filtration kettle;
the filter pressing kettles are connected with an air compressor, and a plurality of filter pressing kettles are connected in parallel;
the first suction filtration kettle and the second suction filtration kettle are both connected with a pretreatment vacuum system, and the first suction filtration kettle and the second suction filtration kettle are used in parallel;
the thickener is at least connected with three thickeners in parallel for intermittent use, the thickener is provided with a jacket for heat preservation, and the thickener is connected with high-temperature high-pressure steam for pressure maintaining.
3. The battery grade manganese sulfate production device according to claim 2, wherein the first reaction kettle and the second reaction kettle are connected with the first buffer tank through a filter pressing kettle;
the first buffer tank is connected with the first pump through a third reaction kettle and a fourth reaction kettle respectively;
the second buffer tank is connected with a second suction filtration kettle through a fourth reaction kettle and a fifth reaction kettle respectively, and the second suction filtration kettle is connected with a third buffer tank;
the third buffer tank is connected with the preheater, the preheater is connected with the first mother liquor tank through the first crystallization system, and the preheater is connected with the second crystallization system and the second mother liquor tank through the mixing tank.
4. The battery grade manganese sulfate production device according to claim 3, wherein the primary crystallization system: the device is formed by sequentially connecting the first-stage forced circulation evaporator, the second-stage forced circulation evaporator, the first-stage crystallizer, the second-stage crystallizer, a first thickener, a second thickener, a third thickener and the first centrifuge;
the secondary crystallization system comprises: the three-stage forced circulation evaporator, the four-stage forced circulation evaporator, the three-stage crystallizer, the four-stage crystallizer, the fourth thickener, the fifth thickener, the sixth thickener and the second centrifuge are sequentially connected.
5. A method for producing battery grade manganese sulfate according to any one of claims 1 to 4, characterized by comprising the steps of:
s1: feeding the acid leaching manganese sulfate solution into a first or a second reaction kettle, adding ferric sulfate, keeping the first and the second reaction kettles at a temperature by saturated steam, feeding the solid-liquid phase of the reaction kettle into a filter pressing kettle for filtering after the reaction is finished, filtering out filter residues, and feeding the filtrate into a first buffer tank;
s2: the filtrate in the first buffer tank is sent to a third reaction kettle or a fourth reaction kettle, hydrogen peroxide and manganese hydroxide powder are added, the PH value of the solution is regulated to 5.0, the reaction time is 1h, the solution enters the first suction filtration kettle for filtration after the reaction is finished, filter residues are filtered out, and the filtrate is sent to the second buffer tank;
s3: the filtrate in the second buffer tank is sent to a fourth or fifth reaction kettle, manganese fluoride is added, the fourth reaction kettle and the fifth reaction kettle are insulated by saturated steam, the filtrate enters a second suction filtration kettle for filtration after the reaction is finished, filter residues are filtered out, and the filtrate is sent to a third buffer tank;
s4: the material enters a preheater from a third buffer tank to be preheated to 95-98 ℃, and the preheated material enters a primary crystallization process;
s5: after primary crystallization is completed, the liquid phase is sent into a first mother liquid tank after solid-liquid separation of a first centrifugal machine, wet salt output by the first centrifugal machine is directly dissolved in a mixing tank, the dissolution liquid is continuously subjected to secondary crystallization, mother liquid after solid-liquid separation of a second centrifugal machine is sent into a second mother liquid tank, materials in the second mother liquid tank are sent into the mixing tank, and then the wet salt output by the second centrifugal machine is dried and packaged to obtain the battery-grade manganese sulfate monohydrate product.
6. The method for producing battery grade manganese sulfate according to claim 5,
the PH value of the reaction of the first reaction kettle and the second reaction kettle is 2.0-3.0, the reaction time is 2-3h, and the reaction temperature is 85-90 ℃;
the third and fourth reaction kettles adjust the PH value of the solution to 5.0, and the reaction time is 1h;
the pH value of the solution in the fifth reaction kettle and the solution in the sixth reaction kettle are 4.0-5.0, the reaction time is 2-3h, and the reaction temperature is 60-65 ℃.
7. The method for producing battery grade manganese sulfate according to claim 6, wherein a primary crystallization system and a secondary crystallization system are used for the primary crystallization process and the secondary crystallization process, respectively, wherein:
the crystallization process of the primary crystallization system and the crystallization process of the secondary crystallization system are operated identically, and specifically: the crystallization temperature is 160-180 ℃, the pressure of the evaporating chamber is 0.6-1.0Mpa, and the pressure of the steam which is connected into the thickener is 1.0-1.2Mpa.
8. The method for producing battery grade manganese sulfate according to claim 7, wherein the high temperature condensed water in the primary crystallization process preheats the material in the preheater to 98 ℃, and the high temperature condensed water in the secondary crystallization process dissolves the primary crystalline wet salt in the mixing tank.
9. The method for producing battery grade manganese sulfate according to claim 5, wherein the vapor compressor is centrifugal compression, and a plurality of the vapor compressors are connected in series, and the vapor compressors are used for providing heat sources for the forced circulation evaporators in the primary crystallization system and the secondary crystallization system.
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