CN114590788A - Zero-emission recycling production method of lithium iron phosphate - Google Patents
Zero-emission recycling production method of lithium iron phosphate Download PDFInfo
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- CN114590788A CN114590788A CN202210227796.9A CN202210227796A CN114590788A CN 114590788 A CN114590788 A CN 114590788A CN 202210227796 A CN202210227796 A CN 202210227796A CN 114590788 A CN114590788 A CN 114590788A
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- iron phosphate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- 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
Abstract
The invention discloses a zero-emission method for circularly producing lithium iron phosphate, which comprises the following steps: (1) mixing and reacting ferrous chloride, hydrogen peroxide and hydrochloric acid in water to obtain a ferric chloride solution; (2) mixing and reacting ferric chloride solution, phosphate radical compound and ammonia water in water to obtain ferric phosphate precursor liquid; (3) mixing the iron phosphate precursor solution with lithium salt and a carbon source, and then drying and calcining to obtain lithium iron phosphate; (4) absorbing waste gas generated by drying and calcining to obtain waste water containing ammonium chloride; (5) reacting the waste water containing ammonium chloride with phosphoric acid to generate hydrogen chloride gas and ammonium phosphate, leading the hydrogen chloride gas out to prepare hydrochloric acid, recycling the hydrochloric acid into the step (1), and recycling the reaction finished liquid into the step (2). The invention basically realizes zero emission and raw material recycling of lithium iron phosphate production, solves a problem which puzzles the environmental pollution of lithium iron phosphate production enterprises, and can greatly reduce the production cost.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a method for circularly producing lithium iron phosphate with zero emission.
Background
With the continuous reduction of petroleum resources and the increasing environmental pollution of automobile exhaust gas worldwide, Hybrid Electric Vehicles (HEV) and Electric Vehicles (EV) have attracted attention as a substitute for future fuel-driven automobiles, and a mobile power supply system is one of the key components of the electric automobiles. Therefore, high performance (i.e., high specific energy, long life, safety), low cost, and environmentally friendly batteries will be a major focus and hot spot for the development of the mobile power industry. Lithium ion batteries are a new generation of green high-energy rechargeable batteries that have been developed to meet this demand. It has the advantages of high voltage, small volume, light weight, high specific energy, no memory effect, no pollution, small self-discharge, long service life, etc.
Since 1997, Padhi et al reported that lithium iron phosphate materials with olivine structure can be used as the anode material of lithium ion batteries, and because of the advantages of low price, environmental protection, no pollution, no moisture absorption, good thermal stability and the like, the lithium iron phosphate materials become one of the most potential anode materials at present and are concerned by the majority of scientific research institutions and commercial institutions. In recent years, a lot of research, development and improvement have been made on the material by many researchers, and the material is gradually commercialized and applied to the lithium ion battery market with high capacity, high power and long service life. Lithium iron phosphate represents the future development direction of the anode material of the power battery.
At present, a solid-phase synthesis method is a main method for preparing commercial lithium iron phosphate, but the requirements of a power lithium ion battery are difficult to meet due to the defects of high cost and difficult storage of a ferrous iron source, large particle size, poor uniformity and the like of the synthesized lithium iron phosphate. So that the ferric iron with low price and stable performance is adopted to replace ferrous iron as an iron source, and the synthesized ferric phosphate is used as a precursor to prepare the lithium iron phosphate. The synthesis method of the iron phosphate generally comprises the steps of reacting ferric trichloride or ferric nitrate solution with phosphoric acid, and then decomposing and volatilizing hydrogen chloride or nitric acid at high temperature to obtain the iron phosphate.
However, a large amount of wastewater is generated in the production of lithium iron phosphate, and the wastewater contains available groups such as chloride ions, ammonium radicals and phosphate radicals, so how to recycle the groups solves the problem of wastewater treatment, reduces the production cost, and becomes a big problem for lithium iron phosphate production enterprises.
Disclosure of Invention
The invention aims to provide a method for circularly producing lithium iron phosphate with zero emission, which basically realizes zero emission of lithium iron phosphate production and cyclic utilization of raw materials.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention discloses a zero-emission method for circularly producing lithium iron phosphate, which comprises the following steps:
(1) mixing and reacting ferrous chloride, hydrogen peroxide and hydrochloric acid in water to obtain a ferric chloride solution;
(2) mixing and reacting the ferric chloride solution obtained in the step (1), a phosphate compound and ammonia water in water to obtain ferric phosphate precursor liquid;
(3) mixing the ferric phosphate precursor solution obtained in the step (2) with lithium salt and a carbon source, and then drying and calcining to obtain lithium iron phosphate;
(4) absorbing waste gas generated in the step (3) through drying and calcining to obtain waste water containing ammonium chloride;
(5) and (3) reacting the ammonium chloride-containing wastewater obtained in the step (4) with phosphoric acid to generate hydrogen chloride gas and ammonium phosphate, leading out the hydrogen chloride gas to prepare hydrochloric acid, recycling the hydrochloric acid into the step (1), and recycling the reaction finished solution into the step (2).
As a preferred technical solution, in the step (2), the phosphate compound includes but is not limited to one or more of phosphoric acid, ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and phytic acid.
In the step (2), the addition amount of ammonia water is controlled to adjust the pH value of the system to less than 7.
As a preferable technical scheme, in the step (2), the reaction temperature is-1-80 ℃.
Preferably, in the step (3), the slurry obtained by mixing the iron phosphate precursor solution with the lithium salt and the carbon source is washed and filtered to obtain the wastewater containing ammonium chloride, and the wastewater is combined in the step (5) for treatment.
As a preferable technical scheme, in the step (5), the wastewater containing ammonium chloride is pretreated before reacting with phosphoric acid, and the pretreatment comprises ammonia water pH value adjustment, coagulating sedimentation, filtration, activated carbon adsorption, resin iron removal, and evaporation concentration.
As a preferable technical scheme, in the step (5), the molar ratio of the added phosphoric acid to the ammonium chloride is 0.5-5: 1.
As a preferable technical scheme, in the step (5), the reaction temperature is 10-300 ℃.
In the step (5), the reaction-completed solution is heated and concentrated and then recycled to the step (2).
The invention has the beneficial effects that:
the invention selects ferrous chloride as the initial raw material for producing lithium iron phosphate, the main material contained in the produced waste water and waste gas is ammonium chloride, after the ammonium chloride reacts with phosphoric acid, hydrochloric acid and ammonium phosphate salt required by the production of lithium iron phosphate are exactly generated, and the hydrochloric acid and the ammonium phosphate salt are respectively recycled to the corresponding reaction steps, thereby basically realizing zero emission and raw material recycling of the production of the lithium iron phosphate, solving the problem of disturbing the environmental pollution of lithium iron phosphate production enterprises, greatly reducing the production cost and further realizing greater economic value and environmental protection value.
In addition, the ferric phosphate precursor liquid is directly used for producing the lithium iron phosphate, and compared with the traditional method using ferric phosphate powder raw materials, the method saves the steps of drying and calcining ferric phosphate and greatly saves the production cost.
Drawings
Fig. 1 is a process flow diagram for producing lithium iron phosphate from ferrous chloride.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described with reference to the accompanying drawings.
As shown in fig. 1, lithium iron phosphate is produced by the following steps:
(1) adding ferrous chloride, hydrogen peroxide and hydrochloric acid into a ferric chloride reaction kettle, mixing and stirring for reaction, and pumping the obtained ferric chloride solution into a ferric chloride tank for temporary storage.
(2) Adding a ferric chloride solution, phytic acid, ammonium dihydrogen phosphate and ammonia water into a reaction kettle, controlling the adding amount of the ammonia water to adjust the pH value of the system to about 2, and then mixing and stirring the mixture in the reaction kettle at 20 ℃ for reaction for 1 hour; and pumping the reaction slurry into an aging kettle to age for 1 hour to obtain the ferric phosphate precursor liquid.
(3) Adding lithium carbonate and glucose into an aging kettle, fully mixing and dispersing with the ferric phosphate precursor liquid, and pumping the obtained mixed slurry into a finished product tank for temporary storage; and pumping the mixed slurry into a plate-and-frame filter, filtering, washing to be neutral, adding the wet material into a spray dryer, spray drying, and calcining in a roller kiln to obtain the lithium iron phosphate.
(4) Leading the waste gas dried and calcined in the step (3) out to an absorption tower to be absorbed into waste water containing ammonium chloride, and combining the waste water containing ammonium chloride obtained by filtering in the step (3); the method comprises the following steps of firstly, pretreating the waste water containing ammonium chloride by ammonia water to adjust the pH value, coagulating sedimentation, filtering, adsorbing by activated carbon, removing iron by resin, evaporating and concentrating, and the like, then adding the waste water into an ammonium chloride reactor, adding phosphoric acid into the ammonium chloride reactor according to the molar ratio of 2:1 of phosphoric acid to ammonium chloride, heating the mixture to 40 ℃ for reaction, and reacting to generate hydrogen chloride gas and ammonium phosphate (mainly ammonium dihydrogen phosphate); the reaction formula is as follows: NH (NH)4Cl+H3PO4＝HCI↑+NH4H2PO4；
Leading out hydrogen chloride gas under negative pressure, absorbing the hydrogen chloride gas with water to prepare hydrochloric acid, and recycling the hydrochloric acid to the step (1); and (3) the reaction finished solution mainly contains ammonium dihydrogen phosphate and phosphoric acid, and the ammonium dihydrogen phosphate and the phosphoric acid are recycled to the step (2) after being evaporated and concentrated.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A zero-emission method for circularly producing lithium iron phosphate is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing and reacting ferrous chloride, hydrogen peroxide and hydrochloric acid in water to obtain a ferric chloride solution;
(2) mixing and reacting the ferric chloride solution obtained in the step (1), a phosphate compound and ammonia water in water to obtain ferric phosphate precursor liquid;
(3) mixing the ferric phosphate precursor solution obtained in the step (2) with lithium salt and a carbon source, and then drying and calcining to obtain lithium iron phosphate;
(4) absorbing waste gas generated in the step (3) through drying and calcining to obtain waste water containing ammonium chloride;
(5) and (3) reacting the ammonium chloride-containing wastewater obtained in the step (4) with phosphoric acid to generate hydrogen chloride gas and ammonium phosphate, leading out the hydrogen chloride gas to prepare hydrochloric acid, recycling the hydrochloric acid into the step (1), and recycling the reaction finished solution into the step (2).
2. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (2), the phosphate compound includes, but is not limited to, one or a mixture of several of phosphoric acid, ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and phytic acid.
3. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (2), the pH value of the system is adjusted to be less than 7 by controlling the adding amount of the ammonia water.
4. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (2), the reaction temperature is-1-80 ℃.
5. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: and (3) washing and filtering slurry obtained by mixing the iron phosphate precursor liquid, the lithium salt and the carbon source to obtain the wastewater containing ammonium chloride, and combining the wastewater with the ammonium chloride to be treated in the step (5).
6. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (5), the wastewater containing ammonium chloride is pretreated before reacting with phosphoric acid, wherein the pretreatment comprises ammonia water pH value adjustment, coagulating sedimentation, filtration, activated carbon adsorption, resin iron removal and evaporation concentration.
7. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (5), the molar ratio of the added phosphoric acid to the ammonium chloride is 0.5-5: 1.
8. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (5), the reaction temperature is 10-300 ℃.
9. The method for zero-emission cyclic production of lithium iron phosphate according to claim 1, characterized in that: in the step (5), the reaction finished solution is heated and concentrated and then recycled to the step (2).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115259119A (en) * | 2022-07-06 | 2022-11-01 | 北京水木方科技有限公司 | Method for continuously preparing battery-grade iron phosphate by using ferrous chloride |
| CN115490219A (en) * | 2022-09-02 | 2022-12-20 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060257307A1 (en) * | 2005-05-10 | 2006-11-16 | Aquire Energy Co., Ltd. | Method for making a lithium mixed metal compound |
| CN101121549A (en) * | 2007-07-16 | 2008-02-13 | *** | Method for treating ammonium-containing chlorine-containing waste water and recycling ammonium and chlorine |
| CN103825024A (en) * | 2014-02-24 | 2014-05-28 | 宁波工程学院 | Battery-grade ferric phosphate and preparation method |
| CN103887499A (en) * | 2014-04-04 | 2014-06-25 | 清华大学深圳研究生院 | Iron phosphate, lithium iron phosphate as well as preparation methods of iron phosphate and lithium iron phosphate |
| CN111422851A (en) * | 2020-03-02 | 2020-07-17 | 曲靖市德方纳米科技有限公司 | Lithium iron phosphate and preparation method thereof |
| CN114105115A (en) * | 2021-11-22 | 2022-03-01 | 青岛九环新越新能源科技股份有限公司 | Production method and application of iron phosphate and lithium iron phosphate |
-
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- 2022-03-08 CN CN202210227796.9A patent/CN114590788A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060257307A1 (en) * | 2005-05-10 | 2006-11-16 | Aquire Energy Co., Ltd. | Method for making a lithium mixed metal compound |
| CN101121549A (en) * | 2007-07-16 | 2008-02-13 | *** | Method for treating ammonium-containing chlorine-containing waste water and recycling ammonium and chlorine |
| CN103825024A (en) * | 2014-02-24 | 2014-05-28 | 宁波工程学院 | Battery-grade ferric phosphate and preparation method |
| CN103887499A (en) * | 2014-04-04 | 2014-06-25 | 清华大学深圳研究生院 | Iron phosphate, lithium iron phosphate as well as preparation methods of iron phosphate and lithium iron phosphate |
| CN111422851A (en) * | 2020-03-02 | 2020-07-17 | 曲靖市德方纳米科技有限公司 | Lithium iron phosphate and preparation method thereof |
| CN114105115A (en) * | 2021-11-22 | 2022-03-01 | 青岛九环新越新能源科技股份有限公司 | Production method and application of iron phosphate and lithium iron phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 孟广耀等: "《材料化学若干前沿研究》", 中国科学技术大学出版社, pages: 125 - 126 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115259119A (en) * | 2022-07-06 | 2022-11-01 | 北京水木方科技有限公司 | Method for continuously preparing battery-grade iron phosphate by using ferrous chloride |
| CN115259119B (en) * | 2022-07-06 | 2024-02-27 | 北京水木方科技有限公司 | Method for continuously preparing battery-grade ferric phosphate by using ferrous chloride |
| CN115490219A (en) * | 2022-09-02 | 2022-12-20 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
| CN115490219B (en) * | 2022-09-02 | 2024-03-12 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
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