CN104211029B - A kind of preparation method of lithium hexafluoro phosphate - Google Patents
A kind of preparation method of lithium hexafluoro phosphate Download PDFInfo
- Publication number
- CN104211029B CN104211029B CN201410349454.XA CN201410349454A CN104211029B CN 104211029 B CN104211029 B CN 104211029B CN 201410349454 A CN201410349454 A CN 201410349454A CN 104211029 B CN104211029 B CN 104211029B
- Authority
- CN
- China
- Prior art keywords
- lithium
- hydrogen fluoride
- hexafluoro phosphate
- fluoride
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 title claims 14
- 229910019142 PO4 Inorganic materials 0.000 title claims 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims 14
- 239000010452 phosphate Substances 0.000 title claims 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 64
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000012047 saturated solution Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 3
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 abstract description 41
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012452 mother liquor Substances 0.000 description 10
- 229920002313 fluoropolymer Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SGWCNDDOFLBOQV-UHFFFAOYSA-N oxidanium;fluoride Chemical compound O.F SGWCNDDOFLBOQV-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Abstract
本发明涉及锂电池技术领域，为解决目前六氟磷酸锂的制备过程中反应剧烈、安全性较差的问题，本发明提出了一种六氟磷酸锂的制备方法，（1）对无水氟化氢进行精馏纯化，得到高纯度无水氟化氢；（2）将氟化锂溶解于高纯度无水氟化氢中，得到含氟化锂的无水氟化氢溶液；（3）加入五氯化磷，制备六氟磷酸锂饱和溶液；（4）将六氟磷酸锂饱和溶液经低温结晶、固液分离、干燥、粉碎包装得到六氟磷酸锂产品；本发明生产工艺简单，安全可靠，原料易得，生产效率高，所得六氟磷酸锂产品纯度高，质量好。The present invention relates to the technical field of lithium batteries. In order to solve the problems of severe reaction and poor safety in the preparation process of lithium hexafluorophosphate, the present invention proposes a preparation method of lithium hexafluorophosphate. (1) Carry out rectification and purification of anhydrous hydrogen fluoride to obtain High-purity anhydrous hydrogen fluoride; (2) dissolving lithium fluoride in high-purity anhydrous hydrogen fluoride to obtain anhydrous hydrogen fluoride solution containing lithium fluoride; (3) adding phosphorus pentachloride to prepare a saturated solution of lithium hexafluorophosphate; (4) The lithium hexafluorophosphate saturated solution is subjected to low-temperature crystallization, solid-liquid separation, drying, crushing and packaging to obtain the lithium hexafluorophosphate product; the production process of the present invention is simple, safe and reliable, the raw materials are easily available, and the production efficiency is high, and the obtained lithium hexafluorophosphate product has high purity and good quality.
Description
技术领域 technical field
本发明涉及锂电池技术领域，具体地说涉及一种高纯度六氟磷酸锂的制备方法。 The invention relates to the technical field of lithium batteries, in particular to a method for preparing high-purity lithium hexafluorophosphate.
背景技术 Background technique
近年来，锂离子电池凭借其能量密度大、工作电压高、自放电小、循环寿命长、无污染等优点，广泛应用于手机、笔记本电脑、摄像机等电子产品上。六氟磷酸锂（LiPF6）是锂离子电池电解液的重要组成物质之一，在有机溶剂中的溶解度、电导率、安全性和环保性最具优势，成为目前应用范围最广的锂盐电解质。但锂离子电池仍存在充电时间、耐高温性等问题点。锂电池生产商为了提高产品的性能和安全性，对六氟磷酸锂（LiPF6）的指标要求也越来越严格。 In recent years, lithium-ion batteries have been widely used in mobile phones, notebook computers, cameras and other electronic products due to their advantages such as high energy density, high working voltage, small self-discharge, long cycle life, and no pollution. Lithium hexafluorophosphate (LiPF 6 ) is one of the important components of lithium-ion battery electrolyte. It has the most advantages in solubility, conductivity, safety and environmental protection in organic solvents, and has become the most widely used lithium salt electrolyte. However, lithium-ion batteries still have problems such as charging time and high temperature resistance. In order to improve the performance and safety of products, lithium battery manufacturers have increasingly strict requirements on lithium hexafluorophosphate (LiPF 6 ).
申请号为201010550107.5的中国发明专利公开了一种六氟磷酸锂的制备方法，该发明利用氟化氢与五氯化磷反应得到五氟化磷与氯化氢的混合气体；将该混合气体通入到氟化氢和氟化锂中，使在一定温度和压力下反应制得六氟磷酸锂溶液；最后结晶分离，过滤干燥得六氟磷酸锂产品。该方法的缺点是采用氟化氢与五氯化磷反应得到五氟化磷，以五氟化磷为合成六氟磷酸锂的原料，但该反应极为剧烈，操作不当容易发生爆炸。 The Chinese invention patent with the application number 201010550107.5 discloses a preparation method of lithium hexafluorophosphate, which uses hydrogen fluoride and phosphorus pentachloride to react to obtain a mixed gas of phosphorus pentafluoride and hydrogen chloride; the mixed gas is passed into hydrogen fluoride and lithium fluoride In the process, react at a certain temperature and pressure to obtain a lithium hexafluorophosphate solution; finally crystallize and separate, filter and dry to obtain a lithium hexafluorophosphate product. The disadvantage of this method is that hydrogen fluoride and phosphorus pentachloride are reacted to obtain phosphorus pentafluoride, and phosphorus pentafluoride is used as a raw material for synthesizing lithium hexafluorophosphate, but the reaction is extremely violent, and improper operation is prone to explosion.
发明内容 Contents of the invention
为解决目前六氟磷酸锂的制备过程中反应剧烈、安全性较差的问题，本发明提出了一种六氟磷酸锂的制备方法，本发明生产工艺简单，安全可靠，原料易得，生产效率高，所得六氟磷酸锂产品纯度高，质量好。 In order to solve the problems of violent reaction and poor safety in the current preparation process of lithium hexafluorophosphate, the present invention proposes a preparation method of lithium hexafluorophosphate. The production process of the present invention is simple, safe and reliable, the raw materials are easy to obtain, and the production efficiency is high. The purity of the obtained lithium hexafluorophosphate product is High and good quality.
本发明是通过以下技术方案实现的：一种六氟磷酸锂的制备方法为以下步骤： The present invention is achieved through the following technical solutions: a preparation method of lithium hexafluorophosphate comprises the following steps:
（1）对无水氟化氢进行精馏纯化，得到高纯度无水氟化氢； (1) Perform rectification and purification of anhydrous hydrogen fluoride to obtain high-purity anhydrous hydrogen fluoride;
作为优选，精馏后高纯度无水氟化氢中水分含量为1~20ppm，金属离子含量低于10ppb； Preferably, the moisture content in the high-purity anhydrous hydrogen fluoride after rectification is 1-20ppm, and the metal ion content is lower than 10ppb;
（2）将氟化锂溶解于步骤（1）的高纯度无水氟化氢中，得到含氟化锂的无水氟化氢溶液； (2) dissolving lithium fluoride in the high-purity anhydrous hydrogen fluoride in step (1) to obtain an anhydrous hydrogen fluoride solution containing lithium fluoride;
因氟化锂的溶解过程会释放大量的热，需对反应容器进行冷却降温，作为优选，溶解过程中温度控制在-20℃~20℃，压力控制在-0.05 Mpa ~0.18Mpa； Because the dissolution process of lithium fluoride will release a lot of heat, the reaction vessel needs to be cooled down. As a preference, the temperature during the dissolution process is controlled at -20°C~20°C, and the pressure is controlled at -0.05 Mpa ~0.18Mpa;
（3）在步骤（2）制备的溶液中加入五氯化磷，制备六氟磷酸锂饱和溶液； (3) adding phosphorus pentachloride to the solution prepared in step (2) to prepare a saturated lithium hexafluorophosphate solution;
作为优选，氟化锂、五氯化磷、无水氟化氢的质量比为1：5.04~10.45：17.3~37.6。 Preferably, the mass ratio of lithium fluoride, phosphorus pentachloride and anhydrous hydrogen fluoride is 1:5.04~10.45:17.3~37.6.
反应温度控制为-20℃~20℃，压力控制在-0.05 Mpa ~0.4Mpa。 The reaction temperature is controlled at -20°C~20°C, and the pressure is controlled at -0.05Mpa~0.4Mpa.
（4）将六氟磷酸锂饱和溶液经低温结晶、固液分离、干燥、粉碎包装得到六氟磷酸锂产品； (4) Lithium hexafluorophosphate product is obtained by low-temperature crystallization, solid-liquid separation, drying, crushing and packaging of saturated lithium hexafluorophosphate solution;
作为优选，将六氟磷酸锂饱和溶液送入晶析槽，缓慢降温至-80℃以下，析出六氟磷酸锂晶体，再将其进行固液分离，所得的晶体在温度25℃~135℃下进行干燥1~8小时，得到干燥的六氟磷酸锂产品。 Preferably, the saturated solution of lithium hexafluorophosphate is sent into the crystallization tank, and the temperature is slowly lowered to below -80°C to precipitate lithium hexafluorophosphate crystals, which are then subjected to solid-liquid separation, and the obtained crystals are dried at a temperature of 25°C to 135°C for 1 to 8 hours , to obtain dry lithium hexafluorophosphate product.
所述干燥采用将氟化氢蒸发分离的方法，最后经粉碎后得到六氟磷酸锂产品。 The drying adopts the method of evaporative separation of hydrogen fluoride, and finally the lithium hexafluorophosphate product is obtained after crushing.
作为优选，固液分离得到的母液循环利用，加入氟化锂与五氯化磷，制备六氟磷酸锂饱和溶液。 Preferably, the mother liquor obtained by solid-liquid separation is recycled, and lithium fluoride and phosphorus pentachloride are added to prepare a saturated solution of lithium hexafluorophosphate.
与现有技术相比，本发明的有益效果是：本发明生产工艺简单，安全可靠，原料易得，生产效率高，所得六氟磷酸锂产品纯度高，质量好。 Compared with the prior art, the beneficial effects of the present invention are: the production process of the present invention is simple, safe and reliable, the raw materials are easy to obtain, the production efficiency is high, and the obtained lithium hexafluorophosphate product has high purity and good quality.
附图说明 Description of drawings
图1为本发明的流程示意图。 Fig. 1 is a schematic flow chart of the present invention.
具体实施方式 detailed description
下面通过实施例对本发明作进一步详细说明。 The present invention will be described in further detail below by way of examples.
实施例1 Example 1
（1）高纯度氟化氢的制备：在密闭的钢衬氟塑料容器中，加入400kg无水氟化氢，经氟塑料再沸器加热，精馏出的氟化氢气体通过冷凝器冷凝，冷凝温度控制在0℃以下，控制回流比为1~2，获得高纯度无水氟化氢，其中无水氟化氢中水分含量在20ppm，金属离子含量控制在9ppb。 (1) Preparation of high-purity hydrogen fluoride: Add 400kg of anhydrous hydrogen fluoride into a closed steel-lined fluoroplastic container, heat it through a fluoroplastic reboiler, and condense the hydrogen fluoride gas from the rectification through a condenser. The condensation temperature is controlled at 0°C Below, the reflux ratio is controlled at 1~2 to obtain high-purity anhydrous hydrogen fluoride, wherein the water content in anhydrous hydrogen fluoride is 20ppm, and the metal ion content is controlled at 9ppb.
（2）氟化锂溶液的制备：在钢衬氟塑料反应釜中通入高纯氮气以置换反应釜内的空气，加入180kg步骤（1）制备的高纯度无水氟化氢，再通过加料器加入6kg 氟化锂，其中，氟化锂纯度≥99.9%；利用泵进行循环，使氟化锂充分溶解于无水氟化氢中。反应釜夹套通冷冻水，冷冻水温度为7℃，控制反应釜内温度为19℃以下，压力为0.18MPa 。 (2) Preparation of lithium fluoride solution: Introduce high-purity nitrogen into the steel-lined fluoroplastic reactor to replace the air in the reactor, add 180kg of high-purity anhydrous hydrogen fluoride prepared in step (1), and then add it through the feeder 6kg of lithium fluoride, wherein the purity of lithium fluoride is ≥99.9%; the pump is used to circulate, so that lithium fluoride is fully dissolved in anhydrous hydrogen fluoride. The reactor jacket is fed with chilled water, the temperature of the chilled water is 7°C, the temperature inside the reactor is controlled below 19°C, and the pressure is 0.18MPa.
（3）六氟磷酸锂溶液的制备：在步骤（2）所得的氟化锂溶液中，通过加料器缓慢均匀加入48.2kg 五氯化磷；利用泵进行循环，使反应充分进行生成六氟磷酸锂饱和溶液。反应釜夹套通冷冻水，冷冻水温度为-19℃，控制反应过程温度为15℃以下，压力为0.38MPa。反应过程会产生氯化氢气体和氟化氢气体，将该气体通过冷凝器，回收氟化氢气体。 (3) Preparation of lithium hexafluorophosphate solution: Add 48.2 kg of phosphorus pentachloride slowly and evenly through a feeder to the lithium fluoride solution obtained in step (2); circulate with a pump to fully proceed the reaction to form a saturated solution of lithium hexafluorophosphate. The jacket of the reaction kettle is fed with chilled water, the temperature of the chilled water is -19°C, the temperature of the reaction process is controlled below 15°C, and the pressure is 0.38MPa. The reaction process will produce hydrogen chloride gas and hydrogen fluoride gas, and the gas will be passed through the condenser to recover the hydrogen fluoride gas.
（4）结晶分离步骤：将步骤（3）生成的六氟磷酸锂饱和溶液移至晶析槽中进行结晶，最终温度到-30℃，结晶过程结束后，将晶体和液体通过固液分离装置，将液体排至母液槽。晶体转移至干燥装置中，使温度升高至70℃进行干燥5小时，最后经粉碎后得到8.2kg高纯度六氟磷酸锂产品。经过分析，得到产品的纯度99.98%，游离酸为58ppm，不溶物为68ppm。 (4) Crystallization and separation step: move the saturated lithium hexafluorophosphate solution generated in step (3) to a crystallization tank for crystallization, and the final temperature is -30°C. After the crystallization process is completed, pass the crystal and liquid through a solid-liquid separation device, and the liquid Drain to mother liquor tank. The crystals were transferred to a drying device, and the temperature was raised to 70°C for drying for 5 hours, and finally 8.2 kg of high-purity lithium hexafluorophosphate product was obtained after crushing. After analysis, the purity of the product is 99.98%, the free acid is 58ppm, and the insoluble matter is 68ppm.
母液进行回收利用，通过测定母液中六氟磷酸锂的浓度，计算下次氟化锂、五氯化磷以及无水氟化氢的加入量。 The mother liquor is recycled, and the amount of lithium fluoride, phosphorus pentachloride and anhydrous hydrogen fluoride to be added is calculated by measuring the concentration of lithium hexafluorophosphate in the mother liquor.
实施例2 Example 2
（1）高纯度氟化氢的制备：在密闭的钢衬氟塑料容器中，加入400kg无水氟化氢，经氟塑料再沸器加热，精馏出的氟化氢气体通过冷凝器冷凝，冷凝温度控制在-5℃，控制回流比为2~4，获得高纯度无水氟化氢，其中无水氟化氢中水分含量在10ppm，金属离子含量控制在5ppb。 (1) Preparation of high-purity hydrogen fluoride: Add 400kg of anhydrous hydrogen fluoride into a closed steel-lined fluoroplastic container, heat it through a fluoroplastic reboiler, and condense the hydrogen fluoride gas from the rectification through a condenser. The condensation temperature is controlled at -5 ℃, control the reflux ratio to 2~4, and obtain high-purity anhydrous hydrogen fluoride, wherein the water content in anhydrous hydrogen fluoride is 10ppm, and the metal ion content is controlled at 5ppb.
（2）氟化锂溶液的制备：在钢衬氟塑料反应釜中通入高纯氮气以置换反应釜内的空气，加入150kg高纯度无水氟化氢，再通过加料器加入6kg 氟化锂，其中，氟化锂纯度≥99.9%；利用泵进行循环，使氟化锂充分溶解于无水氟化氢中。反应釜夹套通冷冻水，冷冻水温度为-19℃，控制反应釜内温度为0℃，压力为0.05MPa 。 (2) Preparation of lithium fluoride solution: Introduce high-purity nitrogen into the steel-lined fluoroplastic reactor to replace the air in the reactor, add 150kg of high-purity anhydrous hydrogen fluoride, and then add 6kg of lithium fluoride through the feeder, of which , the purity of lithium fluoride is ≥99.9%; the pump is used to circulate, so that lithium fluoride is fully dissolved in anhydrous hydrogen fluoride. The jacket of the reactor is fed with chilled water, the temperature of the chilled water is -19°C, the temperature inside the reactor is controlled at 0°C, and the pressure is 0.05MPa.
（3）六氟磷酸锂溶液的制备：在步骤（2）所得的氟化锂溶液中，通过加料器缓慢均匀加入42kg 五氯化磷；利用泵进行循环，使反应充分进行生成六氟磷酸锂饱和溶液。反应釜夹套通冷冻水，冷冻水温度为-19℃，控制反应过程温度为0℃，压力为0.1MPa。反应过程会产生氯化氢气体和氟化氢气体，将该气体通过冷凝器，回收氟化氢气体。 (3) Preparation of lithium hexafluorophosphate solution: In the lithium fluoride solution obtained in step (2), slowly and uniformly add 42kg of phosphorus pentachloride through a feeder; use a pump to circulate, so that the reaction can fully proceed to form a saturated solution of lithium hexafluorophosphate. The jacket of the reaction kettle is fed with chilled water, the temperature of the chilled water is -19°C, the temperature of the reaction process is controlled at 0°C, and the pressure is 0.1MPa. The reaction process will produce hydrogen chloride gas and hydrogen fluoride gas, and the gas will be passed through the condenser to recover the hydrogen fluoride gas.
（4）结晶分离步骤：将步骤（3）生成的六氟磷酸锂饱和溶液移至晶析槽中进行结晶，最终温度到-40℃，将晶体和液体通过固液分离装置，将液体排至母液槽。晶体转移至干燥装置中，使温度升高至135℃进行干燥1小时，最后经粉碎后得到8.9kg高纯度六氟磷酸锂产品。经过分析，得到产品的纯度99.975%，游离酸为36ppm，不溶物为52ppm。 (4) Crystallization and separation step: move the saturated lithium hexafluorophosphate solution generated in step (3) to a crystallization tank for crystallization, the final temperature is -40°C, pass the crystal and liquid through a solid-liquid separation device, and discharge the liquid to the mother liquor tank. The crystal was transferred to a drying device, and the temperature was raised to 135° C. for drying for 1 hour, and finally, 8.9 kg of high-purity lithium hexafluorophosphate product was obtained after crushing. After analysis, the purity of the product is 99.975%, the free acid is 36ppm, and the insoluble matter is 52ppm.
母液进行回收利用，通过测定母液中六氟磷酸锂的浓度，计算下次氟化锂、五氯化磷以及无水氟化氢的加入量。 The mother liquor is recycled, and the amount of lithium fluoride, phosphorus pentachloride and anhydrous hydrogen fluoride to be added is calculated by measuring the concentration of lithium hexafluorophosphate in the mother liquor.
实施例3 Example 3
（1）高纯度氟化氢的制备：在密闭的钢衬氟塑料容器中，加入400kg无水氟化氢，经氟塑料再沸器加热，精馏出的氟化氢气体通过冷凝器冷凝，冷凝温度控制在0℃以下，控制回流比为3~4，获得高纯度无水氟化氢，其中无水氟化氢中水分含量在1ppm，金属离子含量控制在3ppb。 (1) Preparation of high-purity hydrogen fluoride: Add 400kg of anhydrous hydrogen fluoride into a closed steel-lined fluoroplastic container, heat it through a fluoroplastic reboiler, and condense the hydrogen fluoride gas from the rectification through a condenser. The condensation temperature is controlled at 0°C Below, control the reflux ratio to 3~4 to obtain high-purity anhydrous hydrogen fluoride, wherein the moisture content in anhydrous hydrogen fluoride is 1ppm, and the metal ion content is controlled at 3ppb.
（2）氟化锂溶液的制备：氟化锂溶液的制备：在钢衬氟塑料反应釜中通入高纯氮气以置换反应釜内的空气，加入225.6kg步骤（1）制备的高纯度无水氟化氢，再通过加料器加入6kg 氟化锂，其中，氟化锂纯度≥99.9%；利用泵进行循环，使氟化锂充分溶解于无水氟化氢中。反应釜夹套通冷冻水，冷冻水温度为-19℃，控制反应釜内温度为-10℃，压力为-0.04MPa 。 (2) Preparation of lithium fluoride solution: Preparation of lithium fluoride solution: Introduce high-purity nitrogen into the steel-lined fluoroplastic reactor to replace the air in the reactor, and add 225.6kg of high-purity lithium fluoride prepared in step (1). Water hydrogen fluoride, and then add 6kg lithium fluoride through a feeder, wherein the purity of lithium fluoride is ≥99.9%; use a pump to circulate, so that lithium fluoride is fully dissolved in anhydrous hydrogen fluoride. The reactor jacket is fed with chilled water, the temperature of the chilled water is -19°C, the temperature inside the reactor is controlled at -10°C, and the pressure is -0.04MPa.
（3）六氟磷酸锂溶液的制备：在步骤（2）所得的氟化锂溶液中，通过加料器缓慢均匀加入62.7kg五氯化磷；利用泵进行循环，使反应充分进行生成六氟磷酸锂饱和溶液。反应釜夹套通冷冻水，冷冻水温度为-19℃，控制反应过程温度为-10℃，压力为-0.05MPa。反应过程会产生氯化氢气体和氟化氢气体，将该气体通过冷凝器，回收氟化氢气体。 (3) Preparation of lithium hexafluorophosphate solution: Add 62.7 kg of phosphorus pentachloride slowly and evenly through a feeder to the lithium fluoride solution obtained in step (2); circulate with a pump to fully proceed the reaction to form a saturated solution of lithium hexafluorophosphate. The jacket of the reaction kettle is fed with chilled water, the temperature of the chilled water is -19°C, the temperature of the reaction process is controlled at -10°C, and the pressure is -0.05MPa. The reaction process will produce hydrogen chloride gas and hydrogen fluoride gas, and the gas will be passed through the condenser to recover the hydrogen fluoride gas.
（4）结晶分离步骤：将步骤（3）生成的六氟磷酸锂饱和溶液移至晶析槽中进行结晶，最终温度到-80℃，将晶体和液体通过固液分离装置，将液体排至母液槽。晶体转移至干燥装置中，使温度升高至25℃进行干燥8小时，最后经粉碎后得到9.7kg高纯度六氟磷酸锂产品。经过分析，得到产品的纯度99.97%，游离酸为63ppm，不溶物为75ppm。 (4) Crystallization and separation step: move the saturated lithium hexafluorophosphate solution generated in step (3) to a crystallization tank for crystallization, the final temperature is -80°C, pass the crystal and liquid through a solid-liquid separation device, and discharge the liquid to the mother liquor tank. The crystals were transferred to a drying device, and the temperature was raised to 25° C. for drying for 8 hours. Finally, 9.7 kg of high-purity lithium hexafluorophosphate product was obtained after crushing. After analysis, the purity of the product is 99.97%, the free acid is 63ppm, and the insoluble matter is 75ppm.
母液进行回收利用，通过测定母液中六氟磷酸锂的浓度，计算下次氟化锂、五氯化磷以及无水氟化氢的加入量。 The mother liquor is recycled, and the amount of lithium fluoride, phosphorus pentachloride and anhydrous hydrogen fluoride to be added is calculated by measuring the concentration of lithium hexafluorophosphate in the mother liquor.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410349454.XA CN104211029B (en) | 2014-07-22 | 2014-07-22 | A kind of preparation method of lithium hexafluoro phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410349454.XA CN104211029B (en) | 2014-07-22 | 2014-07-22 | A kind of preparation method of lithium hexafluoro phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104211029A CN104211029A (en) | 2014-12-17 |
| CN104211029B true CN104211029B (en) | 2016-09-07 |
Family
ID=52093009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410349454.XA Active CN104211029B (en) | 2014-07-22 | 2014-07-22 | A kind of preparation method of lithium hexafluoro phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104211029B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108439362A (en) * | 2018-05-18 | 2018-08-24 | 青海聚之源新材料有限公司 | A kind of preparation method of high-end lithium hexafluoro phosphate |
| CN109911852B (en) * | 2019-03-14 | 2023-08-04 | 青海聚之源新材料有限公司 | Waste mother liquor recycling device and recycling method for lithium hexafluorophosphate preparation |
| CN111620356A (en) * | 2020-03-27 | 2020-09-04 | 白银中天化工有限责任公司 | Method for liquid-phase purification of low-grade lithium fluoride |
| CN111977674A (en) * | 2020-08-21 | 2020-11-24 | 湖北迈可凯科技有限公司 | Device and method for continuously preparing lithium fluorosulfonate |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866093A (en) * | 1996-06-26 | 1999-02-02 | Solvay Fluor Und Derivate Gmbh | Method of preparing LiPF6 |
| CN1339401A (en) * | 2001-09-25 | 2002-03-13 | 天津化工研究设计院 | Method for preparing lithium hexafluorophosphate |
| CN1433960A (en) * | 2003-03-08 | 2003-08-06 | 汕头市金光高科有限公司 | Method and equipment for synthesizing hexafluorophosphate |
| CN1962423A (en) * | 2005-11-10 | 2007-05-16 | 比亚迪股份有限公司 | Method for preparing lithium hexafluorophosphate |
| CN101209830A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Method for preparing lithium hexafluorophosphate |
| CN101723346A (en) * | 2009-12-11 | 2010-06-09 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102009972A (en) * | 2010-11-19 | 2011-04-13 | 森田化工(张家港)有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102515133A (en) * | 2011-12-31 | 2012-06-27 | 东莞市东骏新能源科技有限公司 | Preparation method of lithium hexafluorophosphate of lithium ion battery electrolyte |
-
2014
- 2014-07-22 CN CN201410349454.XA patent/CN104211029B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866093A (en) * | 1996-06-26 | 1999-02-02 | Solvay Fluor Und Derivate Gmbh | Method of preparing LiPF6 |
| CN1339401A (en) * | 2001-09-25 | 2002-03-13 | 天津化工研究设计院 | Method for preparing lithium hexafluorophosphate |
| CN1433960A (en) * | 2003-03-08 | 2003-08-06 | 汕头市金光高科有限公司 | Method and equipment for synthesizing hexafluorophosphate |
| CN1962423A (en) * | 2005-11-10 | 2007-05-16 | 比亚迪股份有限公司 | Method for preparing lithium hexafluorophosphate |
| CN101209830A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Method for preparing lithium hexafluorophosphate |
| CN101723346A (en) * | 2009-12-11 | 2010-06-09 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102009972A (en) * | 2010-11-19 | 2011-04-13 | 森田化工(张家港)有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102515133A (en) * | 2011-12-31 | 2012-06-27 | 东莞市东骏新能源科技有限公司 | Preparation method of lithium hexafluorophosphate of lithium ion battery electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104211029A (en) | 2014-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109941982B (en) | Purification method of lithium difluorophosphate | |
| CN106882819B (en) | A kind of lithium hexafluoro phosphate prepares purification process | |
| JP6871412B2 (en) | Method for producing high-purity fluoroethylene carbonate | |
| CN102009972B (en) | Preparation method of lithium hexafluorophosphate | |
| CN113135554A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN102515133A (en) | Preparation method of lithium hexafluorophosphate of lithium ion battery electrolyte | |
| CN104211029B (en) | A kind of preparation method of lithium hexafluoro phosphate | |
| CN104310421A (en) | Preparation method of high-purity lithium tetrafluoroborate | |
| CN101570326A (en) | Preparation method of lithium hexafluorophosphate | |
| CN113044825B (en) | Production process and production system of lithium difluorophosphate | |
| CN104555959A (en) | Method for preparing lithium hexafluorophosphate quickly | |
| CN103071365A (en) | Treatment method for tail gas produced by reaction of sulfonyl chlorination | |
| CN101570327A (en) | Method for producing lithium hexafluorophosphate | |
| CN105859760A (en) | A synthetic method of electronic grade lithium difluoro(oxalato)borate | |
| CN107721878A (en) | A kind of method using fusion-crystallization technology separating-purifying succinonitrile | |
| CN104447828B (en) | A kind of synthesizing progress method of di-oxalate lithium borate | |
| CN102515132A (en) | Method for producing high-purity lithium hexafluorophosphate | |
| CN114538406A (en) | Preparation method of high-purity lithium hexafluorophosphate | |
| CN111017966B (en) | Preparation method for preparing high-purity anhydrous lithium chloride by using butyl lithium residues | |
| CN103342372B (en) | Method for preparing lithium tetrafluoroborate | |
| CN108439362A (en) | A kind of preparation method of high-end lithium hexafluoro phosphate | |
| CN101391762A (en) | A kind of preparation method of high-purity lithium hexafluorophosphate | |
| CN105845931B (en) | A kind of preparation method of lithium hexafluoro phosphate | |
| CN102275894A (en) | Method for preparing lithium hexaflourophosphate | |
| CN110835096A (en) | Method for preparing high-purity anhydrous lithium perchlorate by using battery-grade lithium hydroxide monohydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20141217 Assignee: SHANSHAN ADVANCED MATERIALS (QUZHOU) Co.,Ltd. Assignor: ZHEJIANG DONGFU PLASTIC SCIENCE & TECHNOLOGY CO.,LTD. Contract record no.: 2017330000054 Denomination of invention: Method for preparing lithium hexafluorophosphate Granted publication date: 20160907 License type: Common License Record date: 20170509 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20250221 Address after: 324000 room 322, building 15, Chuncheng Road, green industry cluster district, Quzhou City, Zhejiang Province Patentee after: SIDA FLUORINE PLASTIC CO.,LTD. Country or region after: China Address before: No. 6 Huayin North Road, Quzhou High tech Park, Zhejiang Province 324004 Patentee before: ZHEJIANG DONGFU PLASTIC SCIENCE & TECHNOLOGY CO.,LTD. Country or region before: China |