CN113479935A - Low-cost preparation method of battery-grade trimanganese tetroxide - Google Patents
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Abstract
The invention relates to a preparation method of low-cost battery grade trimanganese tetroxide. The low-cost battery-grade trimanganese tetroxide preparation method replaces the expensive alkalis such as liquid alkali and liquid ammonia with the cheap alkalis such as low-cost key lime, and the like, when the battery is prepared by using the manganous oxide, the alkali and manganese sources are the main raw materials and account for more than 70 percent of the cost, the use of cheap lime as alkali will inevitably result in high calcium content in the system, so that in the system of using liquid alkali or ammonia water system to obtain filtrate containing sodium sulfate and ammonium sulfate, lime is added, through the process of sulfate radical and calcium precipitation, thereby leading hydroxide ions in lime to be brought into a system, removing a small amount of calcium in liquid caustic soda, ammonia water or a mixture of the liquid caustic soda and the ammonia water by using sodium carbonate, fully recycling filtrate water in the process of producing the aquatic mature lime by using the quicklime, and thus, the production cost of preparing battery-grade trimanganese tetroxide from manganese sulfate can be greatly reduced, and the problems of high raw material cost and large wastewater treatment capacity in the prior art of producing battery-grade trimanganese tetroxide from manganese sulfate solution are solved.
Description
Technical Field
The invention relates to the technical field of production of battery-grade trimanganese tetroxide, in particular to a preparation method of low-cost battery-grade trimanganese tetroxide.
Background
The lithium manganate is used as one of lithium battery anode materials, the main raw materials comprise EMD and battery-grade trimanganese tetroxide, the battery-grade trimanganese tetroxide has lower impurity content compared with the battery-grade trimanganese tetroxide, and the lithium manganate prepared by the lithium manganate has better high-temperature cycle performance by combining the characteristics of high tap density, spinel structure and the like, and is more used for preparing power-type lithium manganate.
At present, two production processes of a solution method and a manganese sheet method are mainly used for producing battery-grade trimanganese tetroxide in the industry, the cost of the solution method is mainly concentrated on two main raw materials of manganese salt and alkali, the cost of the manganese sheet method mainly comes from an electrolytic manganese sheet, the comparison of the two cost differences is mainly influenced by the price fluctuation of manganese value and alkali, the fluctuation influence of electrolytic manganese value is the largest, when the manganese value is high, the solution method has certain advantages, but the price is still overhigh compared with the EMD, and the competitive advantage of the battery-grade trimanganese tetroxide is not outstanding; this patent aims at optimizing manganese sulfate solution preparation battery level manganous manganic oxide production technology, and this technology raw materials cost is high, waste water treatment capacity is big and development bottleneck points such as with high costs are mainly solved to improve a high performance-price ratio manganous manganic oxide raw materials, the development in boost power type lithium manganate market for power type lithium manganate market.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of low-cost battery-grade trimanganese tetroxide, which has the advantages of low cost, strong environmental protection and the like, and solves the problems of high raw material cost and large wastewater treatment capacity in the production of battery-grade trimanganese tetroxide by using the existing manganese sulfate solution.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of low-cost battery grade manganous-manganic oxide comprises the following steps:
1) taking liquid alkali or ammonia water or a mixture of the liquid alkali and the ammonia water and manganese sulfate as raw materials, preparing battery-grade trimanganese tetroxide by a chemical precipitation method, and obtaining corresponding filtrate by pressure filtration;
2) adding excessive lime into the filtrate of manganomanganic oxide prepared by liquid alkali or liquid ammonia or the mixture of the liquid alkali and the liquid ammonia;
3) performing solid-liquid separation on the mixed solution obtained in the step (2) by adopting centrifugal separation;
4) adding excessive hydrogen carbonate into the separated liquid alkali or ammonia water or the mixture of the two until no precipitate is generated, and then carrying out solid-liquid separation on the generated precipitate;
5) and (3) recycling the obtained liquid alkali and ammonia water or the mixture of the liquid alkali and the ammonia water to a storage tank, standing for a certain time, and recycling the liquid alkali and the ammonia water as production raw materials to the production of the trimanganese tetroxide for the battery.
Further, the specific preparation process of the step 1 is as follows:
A) taking 14.2L of the purified 100g/L manganese sulfate solution, adding a certain amount of complexing agent, fully stirring for later use, marking as an agent A, taking 4L of 32% caustic soda liquid, marking as an agent B for later use;
B) adding a certain amount of base solution into a 30L synthesis kettle, heating to a certain temperature, simultaneously pumping the agent A and the agent B into a synthesis tank by a peristaltic pump under the action of stirring, introducing a certain amount of air in the process, and controlling the pH value;
C) and after the synthesis is finished, carrying out solid-liquid separation on the reaction mixed liquid, washing and drying solid residues, marking as a sample C, and detecting related indexes.
Further, the specific preparation process of the steps 2) and 3) is as follows:
10L of filtrate is taken, 600g of quicklime (excessive lime) is added, stirring is carried out for a certain time to carry out full reaction, and then a centrifuge is used for carrying out solid-liquid separation on the mixture.
Further, the specific preparation process of the step 1 is as follows:
D) taking 14.2L of the purified 100g/L manganese sulfate solution, adding a certain amount of complexing agent, fully stirring for later use, marking as an agent A, taking 8L of 50% ammonia, marking as an agent B for later use;
E) adding a certain amount of base solution into a 30L fully-closed synthesis kettle, heating to a certain temperature, simultaneously pumping the agent A and the agent B into a synthesis tank by a peristaltic pump under the action of stirring, introducing a certain amount of air in the process, and controlling the pH value;
F) and after the synthesis is finished, carrying out solid-liquid separation on the reaction mixed liquid, washing and drying solid residues, marking as a sample A, and detecting related indexes.
Further, the specific preparation process of the steps 2) and 3) is as follows:
taking 10L of filtrate, adding 600g of quicklime (excessive lime), stirring for a certain time in a closed state for full reaction, and then carrying out solid-liquid separation on the mixture by using a centrifugal machine.
Further, the specific preparation process of the steps 4 and 5 is as follows:
taking 5L of the separated clear liquid, adding excessive sodium carbonate, about 0.5g based on the fact that no precipitate is generated, fully stirring, filtering with a centrifuge, standing the obtained liquid caustic soda for 24 hours, and taking the supernatant for later use.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
1. according to the preparation method of the low-cost battery-grade trimanganese tetroxide, a small amount of calcium hydroxide in liquid alkali or ammonia water is added with excessive sodium carbonate, then the calcium carbonate is removed in a solid-liquid separation mode, the key point that the sodium carbonate can be excessive is that the synthesis is not basically influenced, and the finally recycled liquid alkali or ammonia water cannot absolutely avoid calcium carbonate precipitates, so that the calcium carbonate is separated in a standing mode, quicklime is used, and the reaction with the water in filtrate is a saving key point, compared with the liquid alkali and the ammonia water, the water is continuously introduced from the outside to enter a production system, the problem can not be caused by adding lime, the discharge amount of wastewater is greatly reduced, the water amount accounts for 30% of the total water amount in production statistics, and therefore, the production cost of preparing the battery-grade trimanganese tetroxide from manganese sulfate can be greatly reduced, and the practicability is strong.
2. According to the preparation method of the low-cost battery grade trimanganese tetroxide, high-salt filtrate generated in the production process of the battery grade trimanganese tetroxide is converted into liquid alkali or a mixture of ammonia water and calcium salt through reaction by lime or low-price alkali, and the calcium salt is precipitated to facilitate solid-liquid separation.
3. According to the preparation method of the low-cost battery grade manganous-manganic oxide, a centrifugal filtration mode is adopted for solid-liquid separation of liquid alkali or a mixture of ammonia water and calcium salt, so that the liquid content of solid can be reduced, the alkali recovery rate can be improved, and the separation safety is ensured to a great extent.
Drawings
FIG. 1 is a flow chart of the low-cost battery grade manganous-manganic oxide preparation process of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: a preparation method of low-cost battery grade manganous-manganic oxide comprises the following steps:
1) taking 14.2L of the purified 100g/L manganese sulfate solution, adding a certain amount of complexing agent, fully stirring for later use, marking as an agent A, taking 4L of 32% caustic soda liquid, marking as an agent B for later use;
2) adding a certain amount of base solution into a 30L synthesis kettle, heating to a certain temperature, simultaneously pumping the agent A and the agent B into a synthesis tank by a peristaltic pump under the action of stirring, introducing a certain amount of air in the process, and controlling the pH value;
3) after the synthesis is finished, carrying out solid-liquid separation on the reaction mixed liquid, washing and drying solid residues, marking as a sample C, and detecting related indexes;
4) taking 10L of the filtrate separated in the step 3, adding 600g of quicklime (excessive lime), stirring for a certain time to perform full reaction, and then performing solid-liquid separation on the mixture by using a centrifugal machine;
5) taking 5L of the clear liquid separated in the step 4, adding excessive sodium carbonate, taking the addition as the basis of stopping adding the sodium carbonate to generate no precipitate, wherein the addition is about 0.5g, filtering the mixture by using a centrifugal machine after fully stirring, and taking the supernatant for later use after the obtained liquid caustic soda is kept stand for 24 hours;
6) and (3) detecting the liquid caustic soda obtained in the step (5) through the products obtained in the steps (1), (2) and (3), and comparing with the sample C, wherein the main indexes are basically consistent.
The battery-grade manganous-manganic oxide is prepared by a chemical precipitation method, the used alkali is liquid alkali or ammonia water (or a mixture of the liquid alkali and the ammonia water), the synthesized mixture is subjected to filter pressing separation to obtain a high-salt solution containing sodium sulfate or ammonium sulfate, lime or low-price alkali is added to convert the high-salt solution into the mixture of the liquid alkali or the ammonia water and calcium salt, calcium salt precipitation is separated to obtain a liquid alkali or ammonia water (or a mixture of the liquid alkali and the ammonia water) mixed solution containing trace calcium, finally, the trace calcium hydroxide is removed by adding excessive sodium carbonate, and the liquid alkali or the ammonia water (the mixture of the liquid alkali and the ammonia water) is recycled to a production system after standing.
Example two: a preparation method of low-cost battery grade manganous-manganic oxide comprises the following steps:
1) taking 14.2L of the purified 100g/L manganese sulfate solution, adding a certain amount of complexing agent, fully stirring for later use, marking as an agent A, taking 8L of 50% ammonia, marking as an agent B for later use;
2) adding a certain amount of base solution into a 30L fully-closed synthesis kettle, heating to a certain temperature, simultaneously pumping the agent A and the agent B into a synthesis tank by a peristaltic pump under the action of stirring, introducing a certain amount of air in the process, and controlling the pH value;
3) after the synthesis is finished, carrying out solid-liquid separation on the reaction mixed liquid, washing and drying solid residues, marking as a sample A, and detecting related indexes;
4) taking 10L of the filtrate separated in the step 3, adding 600g of quicklime (excessive lime), stirring in a closed state for a certain time to perform full reaction, and then performing solid-liquid separation on the mixture by using a centrifugal machine;
5) taking 5L of the clear liquid separated in the step 4, adding excessive sodium carbonate, taking the addition as the basis of stopping adding the sodium carbonate to generate no precipitate, wherein the addition is about 0.5g, filtering the mixture by using a centrifugal machine after fully stirring, and taking the supernatant for later use after the obtained liquid caustic soda is kept stand for 24 hours;
6) and (3) detecting the liquid caustic soda obtained in the step (5) through the products obtained in the steps (1), (2) and (3), comparing with the sample A, wherein the main indexes are basically consistent, and the S index has a certain difference.
The battery-grade manganous-manganic oxide is prepared by a chemical precipitation method, the used alkali is liquid alkali or ammonia water (or a mixture of the liquid alkali and the ammonia water), the synthesized mixture is subjected to filter pressing separation to obtain a high-salt solution containing sodium sulfate or ammonium sulfate, lime or low-price alkali is added to convert the high-salt solution into the mixture of the liquid alkali or the ammonia water and calcium salt, calcium salt precipitation is separated to obtain a liquid alkali or ammonia water (or a mixture of the liquid alkali and the ammonia water) mixed solution containing trace calcium, finally, the trace calcium hydroxide is removed by adding excessive sodium carbonate, and the liquid alkali or the ammonia water (the mixture of the liquid alkali and the ammonia water) is recycled to a production system after standing.
The method is characterized in that the main raw materials of the currently used liquid caustic soda and liquid ammonia or the mixture of the liquid caustic soda and the liquid ammonia are recycled by adopting cheaper lime, and the essence is that hydroxide radicals in hydrated lime are utilized to precipitate manganese; calcium ions brought by lime react with sulfate radicals to generate precipitates, so that the sulfate radicals in the filtrate are taken away from the residues, sodium, ammonium and hydroxyl radicals form liquid alkali or ammonia water in the solution, and a small amount of calcium remaining in the alkali solution is precipitated and removed through excessive sodium carbonate; the two aspects can greatly reduce the production cost of preparing the battery-grade trimanganese tetroxide by a solution method adopted in the current industry, and the two aspects relate to the following chemical equations:
main reaction: MnS04+2NaOH＝Mn(OH)2+Na2SO4
6Mn(OH)2+O2＝2Mn3O4+6H2O (complex reaction is slight)
Alkali recovery: na (Na)2SO4+CaO+H20＝CaSO4+2NaOH
CaSO4+Na2CO3＝CaCO3+Na2SO4(reaction type for removing impurities)
In the case of ammonia, the equation is similar.
The invention has the beneficial effects that: the low-cost battery-grade manganous-manganic oxide preparation method is characterized in that excessive sodium carbonate is added into a small amount of calcium hydroxide in liquid alkali or ammonia water, then solid-liquid separation is carried out to remove the calcium carbonate, the key point that the sodium carbonate can be excessive is that the synthesis is basically not influenced, the finally recycled liquid alkali or ammonia water can not absolutely avoid calcium carbonate precipitate, therefore, the separation is carried out by adopting a standing mode, the quicklime reacts with the water in the filtrate through the reaction, which is the key for saving, compared with liquid caustic soda and ammonia water, the quicklime is continuously brought into water from the outside and enters a production system, the problems can not be caused by adding the lime, the discharge amount of wastewater is greatly reduced, the production statistics shows that the water accounts for 30 percent of the total water amount, and thus, the method can greatly reduce the production cost of preparing the battery-grade trimanganese tetroxide from manganese sulfate, has strong practicability, and solves the problems of high raw material cost and large wastewater treatment capacity of the existing manganese sulfate solution for producing the battery-grade trimanganese tetroxide.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A preparation method of low-cost battery grade manganous-manganic oxide is characterized by comprising the following steps:
1) taking liquid alkali or ammonia water or a mixture of the liquid alkali and the ammonia water and manganese sulfate as raw materials, preparing battery-grade trimanganese tetroxide by a chemical precipitation method, and obtaining corresponding filtrate by pressure filtration;
2) adding excessive lime into the filtrate of manganomanganic oxide prepared by liquid alkali or liquid ammonia or the mixture of the liquid alkali and the liquid ammonia;
3) performing solid-liquid separation on the mixed solution obtained in the step (2) by adopting centrifugal separation;
4) adding excessive hydrogen carbonate into the separated liquid alkali or ammonia water or the mixture of the two until no precipitate is generated, and then carrying out solid-liquid separation on the generated precipitate;
5) and (3) recycling the obtained liquid alkali and ammonia water or the mixture of the liquid alkali and the ammonia water to a storage tank, standing for a certain time, and recycling the liquid alkali and the ammonia water as production raw materials to the production of the trimanganese tetroxide for the battery.
2. The method of claim 1, wherein the method comprises the following steps: the specific preparation process of the step 1 comprises the following steps:
A) taking 14.2L of the purified 100g/L manganese sulfate solution, adding a certain amount of complexing agent, fully stirring for later use, marking as an agent A, taking 4L of 32% caustic soda liquid, marking as an agent B for later use;
B) adding a certain amount of base solution into a 30L synthesis kettle, heating to a certain temperature, simultaneously pumping the agent A and the agent B into a synthesis tank by a peristaltic pump under the action of stirring, introducing a certain amount of air in the process, and controlling the pH value;
C) and after the synthesis is finished, carrying out solid-liquid separation on the reaction mixed liquid, washing and drying solid residues, marking as a sample C, and detecting related indexes.
3. The method of claim 2, wherein the step of preparing low-cost battery grade trimanganese tetroxide comprises the following steps: the specific preparation process of the steps 2) and 3) is as follows:
10L of filtrate is taken, 600g of quicklime (excessive lime) is added, stirring is carried out for a certain time to carry out full reaction, and then a centrifuge is used for carrying out solid-liquid separation on the mixture.
4. The method of claim 1, wherein the method comprises the following steps: the specific preparation process of the step 1 comprises the following steps:
D) taking 14.2L of the purified 100g/L manganese sulfate solution, adding a certain amount of complexing agent, fully stirring for later use, marking as an agent A, taking 8L of 50% ammonia, marking as an agent B for later use;
E) adding a certain amount of base solution into a 30L fully-closed synthesis kettle, heating to a certain temperature, simultaneously pumping the agent A and the agent B into a synthesis tank by a peristaltic pump under the action of stirring, introducing a certain amount of air in the process, and controlling the pH value;
F) and after the synthesis is finished, carrying out solid-liquid separation on the reaction mixed liquid, washing and drying solid residues, marking as a sample A, and detecting related indexes.
5. The method of claim 4, wherein the step of preparing low-cost battery grade trimanganese tetroxide comprises the following steps: the specific preparation process of the steps 2) and 3) is as follows:
taking 10L of filtrate, adding 600g of quicklime (excessive lime), stirring for a certain time in a closed state for full reaction, and then carrying out solid-liquid separation on the mixture by using a centrifugal machine.
6. The method of claim 3 or 5, wherein the step of preparing the low-cost battery grade trimanganese tetroxide comprises the following steps: the specific preparation process of the steps 4 and 5 comprises the following steps:
taking 5L of the separated clear liquid, adding excessive sodium carbonate, about 0.5g based on the fact that no precipitate is generated, fully stirring, filtering with a centrifuge, standing the obtained liquid caustic soda for 24 hours, and taking the supernatant for later use.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885845A (en) * | 1993-12-22 | 1999-03-23 | Nippon Sanso Corporation | Method for detecting inorganic hydrides, inorganic halides and organometallic compounds in a gas using copper hydroxide |
| US20120207666A1 (en) * | 2010-08-18 | 2012-08-16 | American Manganese, Inc. | Processing of manganous sulphate/dithionate liquors derived from manganese resource material |
| CN103122411A (en) * | 2013-02-05 | 2013-05-29 | 中南大学 | Cyclic and comprehensive utilization method of sodium-free mangano-manganic oxide production mother solution |
| CN105417586A (en) * | 2015-12-29 | 2016-03-23 | 中国科学院过程工程研究所 | Preparation method for manganic manganous oxide |
| CN107540021A (en) * | 2016-06-23 | 2018-01-05 | 中国科学院过程工程研究所 | Mangano-manganic oxide compound, preparation method containing non-manganese element, the reaction system used and application thereof |
| CN110066647A (en) * | 2018-01-22 | 2019-07-30 | 中国石油化工股份有限公司 | A kind of drilling well stagnation of the circulation of vital energy plug resistant to high temperatures and preparation method thereof |
| CN110835269A (en) * | 2019-10-30 | 2020-02-25 | 安徽朗基新材料科技有限公司 | Production process of high-strength high-performance soft magnetic ferrite material |
| CN111186862A (en) * | 2020-02-27 | 2020-05-22 | 广西锰华新能源科技发展有限公司 | Preparation method of battery-grade high-purity trimanganese tetroxide |
| CN111592148A (en) * | 2020-06-08 | 2020-08-28 | 导洁(北京)环境科技有限公司 | Process method for converting high-salinity wastewater into NaOH solution |
| CN112095017A (en) * | 2020-09-15 | 2020-12-18 | 中南大学 | Method for recycling fly ash based on reduction roasting-acid leaching |
-
2021
- 2021-07-13 CN CN202110789416.6A patent/CN113479935A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885845A (en) * | 1993-12-22 | 1999-03-23 | Nippon Sanso Corporation | Method for detecting inorganic hydrides, inorganic halides and organometallic compounds in a gas using copper hydroxide |
| US20120207666A1 (en) * | 2010-08-18 | 2012-08-16 | American Manganese, Inc. | Processing of manganous sulphate/dithionate liquors derived from manganese resource material |
| CN103122411A (en) * | 2013-02-05 | 2013-05-29 | 中南大学 | Cyclic and comprehensive utilization method of sodium-free mangano-manganic oxide production mother solution |
| CN105417586A (en) * | 2015-12-29 | 2016-03-23 | 中国科学院过程工程研究所 | Preparation method for manganic manganous oxide |
| CN107540021A (en) * | 2016-06-23 | 2018-01-05 | 中国科学院过程工程研究所 | Mangano-manganic oxide compound, preparation method containing non-manganese element, the reaction system used and application thereof |
| CN110066647A (en) * | 2018-01-22 | 2019-07-30 | 中国石油化工股份有限公司 | A kind of drilling well stagnation of the circulation of vital energy plug resistant to high temperatures and preparation method thereof |
| CN110835269A (en) * | 2019-10-30 | 2020-02-25 | 安徽朗基新材料科技有限公司 | Production process of high-strength high-performance soft magnetic ferrite material |
| CN111186862A (en) * | 2020-02-27 | 2020-05-22 | 广西锰华新能源科技发展有限公司 | Preparation method of battery-grade high-purity trimanganese tetroxide |
| CN111592148A (en) * | 2020-06-08 | 2020-08-28 | 导洁(北京)环境科技有限公司 | Process method for converting high-salinity wastewater into NaOH solution |
| CN112095017A (en) * | 2020-09-15 | 2020-12-18 | 中南大学 | Method for recycling fly ash based on reduction roasting-acid leaching |
Non-Patent Citations (3)
| Title |
|---|
| 李美娴等: "高浓度含锰废水的处理及资源化利用", 《中国锰业》 * |
| 许乃才: "《 MnCO3微球的可控制备、表征及高温热分解行为》", 《材料导报》 * |
| 陈飞宇: "《硫酸锰溶液制备电子级四氧化三锰的研究》", 《中国锰业》 * |
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