WO2023226243A1 - Method for preparing lithium hexafluorophosphate by dry method - Google Patents

Method for preparing lithium hexafluorophosphate by dry method Download PDF

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Publication number
WO2023226243A1
WO2023226243A1 PCT/CN2022/118655 CN2022118655W WO2023226243A1 WO 2023226243 A1 WO2023226243 A1 WO 2023226243A1 CN 2022118655 W CN2022118655 W CN 2022118655W WO 2023226243 A1 WO2023226243 A1 WO 2023226243A1
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Prior art keywords
lithium hexafluorophosphate
iodine
lithium fluoride
lithium
foam glass
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PCT/CN2022/118655
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French (fr)
Chinese (zh)
Inventor
傅少鹏
谢光明
张德益
傅艳琼
丘银云
陈颂美
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福建省龙德新能源有限公司
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Publication of WO2023226243A1 publication Critical patent/WO2023226243A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/005—Lithium hexafluorophosphate
    • 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

Definitions

  • the invention belongs to the field of preparing lithium hexafluorophosphate, and in particular relates to a dry method for preparing lithium hexafluorophosphate.
  • Lithium hexafluorophosphate (LiPF 6 ) is a common and commonly used lithium salt for lithium-ion battery electrolytes, and tests have proven that it has the best overall performance and the best use effect among the many lithium-ion battery electrolyte lithium salts currently. For this reason, the production and preparation of lithium hexafluorophosphate has always been a research hotspot.
  • Dry preparation is a traditional method for preparing lithium hexafluorophosphate.
  • the dry method includes two methods: gas-solid method and hydrogen fluoride solvent method.
  • the gas-solid method is more traditional and simple, with high production efficiency. It directly introduces high-temperature phosphorus pentafluoride gas into a sealed container containing lithium fluoride, and reacts under high temperature and high pressure to obtain the lithium hexafluorophosphate product.
  • this method has a low conversion rate of lithium fluoride, and the actual product lithium hexafluorophosphate contains a large amount of lithium fluoride impurities and has low purity.
  • the hydrogen fluoride solvent method places lithium fluoride in anhydrous hydrogen fluoride to make it porous, and at the same time introduces low-flow phosphorus pentafluoride gas for reaction.
  • This method overcomes the low conversion rate and low product conversion rate of the more traditional gas-solid method.
  • the disadvantage of low purity is that anhydrous hydrogen fluoride is used in this solution, which is extremely volatile and corrosive and highly harmful. There are major safety hazards in the production process, and the entire reaction needs to be carried out at low temperature. High energy consumption.
  • the present invention provides a method for dry preparation of lithium hexafluorophosphate.
  • the objects of the present invention are: 1. to improve the preparation efficiency of lithium hexafluorophosphate prepared by dry method; 2. to improve the purity of the obtained lithium hexafluorophosphate product; 3. to avoid the use of hydrogen fluoride and improve the safety of preparation.
  • the present invention adopts the following technical solutions.
  • a method for preparing lithium hexafluorophosphate by dry method includes: 1) using foam glass as a carrier, in an open container, mix lithium fluoride powder and iodine and place it under the foam glass carrier, and then use iodine evaporation after heating method to realize the loading of lithium fluoride on the foam glass to obtain a porous composite intermediate; 2) Place the porous composite intermediate in a sealed reaction vessel, introduce phosphorus pentafluoride gas to react, and achieve the conversion of lithium fluoride to obtain the pre-formed composite intermediate. The product is placed in an organic solvent for ultrasonic treatment, and the precipitate at the bottom of the organic solvent is collected to obtain lithium hexafluorophosphate.
  • lithium fluoride is first loaded into the channels of foam glass with a uniform porous structure through iodine evaporation. At the same time, after the iodine comes into contact with the foam glass, it condenses when cold and acts as an adhesive to achieve fluorine removal. Fix lithium fluoride to avoid loss of lithium fluoride. In the subsequent process, a traditional gas-solid method was adopted to control the flow of phosphorus pentafluoride gas through the porous composite intermediate.
  • the phosphorus pentafluoride gas and lithium fluoride have a more sufficient reaction time.
  • lithium fluoride is loaded on the pore structure and has a huge specific surface area, that is, it actually has a larger reaction area, can react more effectively and fully, and improves the reaction efficiency.
  • specific organic solvents are selected to dissolve and remove iodine while ensuring that lithium hexafluorophosphate remains insoluble, and the carrier and product are separated through an ultrasonic process. Therefore, for the technical solution of the present invention, foam glass, which is reaction inert during the entire reaction process and has unique structural characteristics, and iodine evaporation are the core to realize the entire solution.
  • the foam glass in step 1) is open-cell foamed silica, with an opening rate ⁇ 50%; the foam glass is plate-shaped and/or lamellar-shaped, and is arranged in an open container for opening The opening of the container is closed, allowing the iodine vapor to flow toward the foam glass.
  • foam glass can be prepared using mesoporous silica.
  • Mesoporous silica has good reaction inertness, does not participate in reactions, and has a rich porous structure.
  • the opening of the open container is closed with foam glass, making it a necessary path for the flow of iodine vapor to achieve a stable load of lithium fluoride.
  • the purpose of using an open container is to form a stable air flow and avoid the occurrence of high-pressure conditions. In addition, it can keep the foam glass at a relatively low temperature without cooling, and effectively achieve the condensation of iodine vapor.
  • silica itself does not have very excellent thermal conductivity. If porous metal plates or foam metals are used, not only is it easy to introduce impurities through thermal diffusion, but more importantly, its own heat transfer efficiency is high, which can easily lead to carrier
  • the side facing downwards acts as a "loading surface” because its heat will be quickly exported outwards, causing the temperature of the lower side to always remain low, making it easy for iodine to condense and "capture” and “bond” lithium fluoride. Powders, and a large amount of adhesion load in the surface area will cause stacking, resulting in a drastic decrease in the actual product purity.
  • the mesh number of the lithium fluoride powder described in step 1) is ⁇ 200 mesh.
  • the mass ratio of the lithium fluoride powder and iodine in step 1) is 1: (0.2-0.3); the volume ratio of the foam glass to the bulk volume of the mixed powder of lithium fluoride and iodine is 1: (0.02 ⁇ 0.05).
  • the amount of iodine should not be too large to avoid blocking the pores or causing iodine to be wrapped outside the lithium fluoride, resulting in Reduce lithium fluoride conversion rate or conversion efficiency.
  • controlling the ratio of the volume of the foam glass to the bulk volume of the powder is to ensure that the volume of the foam glass has enough content space for the deposition of lithium fluoride.
  • the foam glass actually has a certain effect of blocking gas circulation, the foam If the glass volume is too large, it will create a greater gas exchange obstruction, which will eventually cause the pressure on the inside/low side of the container (that is, the side used to store powder relative to the position of the foam glass) to increase, resulting in an increase in vapor pressure and inability to effectively achieve iodine release. sublimation.
  • the heating temperature in step 1) is controlled to be 45 to 75°C.
  • Controlling the above-mentioned heating temperature can effectively and stably generate an iodine vapor flow, which is used to carry lithium fluoride and achieve adhesion at the same time.
  • the temperature should be controlled to be ⁇ 55°C to avoid large-area condensation deposition of elemental iodine on the lower side of the carrier.
  • the flow rate of the phosphorus pentafluoride gas in step 2) is controlled at 200-500 mL/min.
  • Controlling the above flow rate of phosphorus pentafluoride gas can improve the utilization rate of phosphorus pentafluoride gas and ensure high reaction efficiency.
  • the phosphorus pentafluoride gas is introduced into a sealed reaction vessel, which has a gas outlet end on the opposite side of the gas inlet end, and the pressure in the sealed reaction vessel is controlled to maintain 1.15-1.25 atm.
  • nitrogen gas preheated to 45-50°C can also be passed between the phosphorus pentafluoride gas for pre-purging.
  • the pre-purging can take away a small amount of trace iodine elements attached to the surface of lithium fluoride.
  • controlling the pressure in the reaction vessel is also about controlling the sublimation of iodine.
  • the organic solvent in step 2) is alcohol.
  • Alcohol can effectively dissolve elemental iodine and achieve separation of the product and carrier. At the same time, lithium hexafluorophosphate is insoluble in alcohol. Therefore, extremely high-purity solid products can be obtained directly without further recrystallization and other operations, which greatly improves the efficiency of production and preparation.
  • the beneficial effects of the present invention are: 1) The advantages of the existing two dry processes for preparing lithium hexafluorophosphate are combined with the template method, and at the same time it effectively overcomes the defects of the two existing dry processes; 2) The overall process flow is efficient, It has extremely high preparation efficiency, and the purity of the obtained product can reach more than 99.5%; 3) The solution is green and pollution-free. The phosphorus pentafluoride tail gas can be easily recovered and trace amounts of iodine vapor can be separated and recycled, and the recycling rate of each material is high. ; 4) The overall process is safe, suitable for large-scale popularization and use, and avoids the use of hydrogen fluoride, greatly reducing costs.
  • Figure 1 is a schematic diagram of the process of loading lithium fluoride and converting to lithium hexafluorophosphate in the present invention
  • Figure 2 is a schematic diagram of the process of loading lithium fluoride and converting to lithium hexafluorophosphate in Comparative Example 1.
  • connection In the present invention, unless otherwise clearly stated and limited, the terms “installation”, “connection”, “connection”, “fixing” and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated; it can be mechanically connected, electrically connected or communicable with each other; it can be directly connected or indirectly connected through an intermediate medium; it can be the internal connection of two elements or the interaction between two elements, Unless otherwise expressly limited. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
  • the raw materials used in the examples of the present invention are all commercially available or those available to those skilled in the art.
  • the methods used in the examples of the present invention are all methods mastered by those skilled in the art.
  • Embodiment 1 A method for preparing lithium hexafluorophosphate by dry method, the method includes: 1) using a mesoporous silica plate with an opening rate of ⁇ 50% as a carrier, and the mesoporous silica plate porosity is 36 to 38% , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top.
  • the gas outlet is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine.
  • the remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.2 atm through the pumping rate of the gas outlet to realize lithium fluoride.
  • a mesoporous silica plate loaded with lithium hexafluorophosphate was obtained.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate was placed in ethanol.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate was completely immersed in ethanol and then subjected to ultrasonic treatment. , until no dust falls, collect the ethanol bottom precipitate, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
  • the yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out.
  • Embodiment 2 A method for preparing lithium hexafluorophosphate by dry method.
  • the method includes: 1) using a mesoporous silica plate with an opening ratio of ⁇ 50% as a carrier, and the mesoporous silica plate porosity is 36 to 38%. , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.2, totaling 6 dm 3.
  • iodine particles are first evenly spread on the bottom of the furnace, and then lithium fluoride powder is evenly spread, and then heated to 55°C and kept at a constant temperature until no powder is visible at the bottom of the furnace, that is, the carrier is recovered to obtain a porous composite intermediate;
  • 2 Place the porous composite intermediate in the middle of the sealed reaction vessel, with an air inlet at one end and a gas outlet at one end on both sides of the plate.
  • the air inlet is fed with phosphorus pentafluoride gas at 10 L/min for reaction, and the output
  • the gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine.
  • the remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.15 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride.
  • a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
  • the yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out.
  • Embodiment 3 A method for preparing lithium hexafluorophosphate by dry method, the method includes: 1) using a mesoporous silica plate with an opening rate of ⁇ 50% as a carrier, and the mesoporous silica plate porosity is 36 to 38% , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.3, totaling 15 dm 3 .
  • the remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.25 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride.
  • a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
  • the yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out.
  • Embodiment 4 A method for preparing lithium hexafluorophosphate by dry method.
  • the method includes: 1) using a mesoporous silica plate with an opening rate of ⁇ 50% as a carrier, and the mesoporous silica plate porosity is 36 to 38%. , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top.
  • the air inlet is fed with phosphorus pentafluoride gas at 12 L/min for reaction, and the output
  • the gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine.
  • the remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.15 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride.
  • a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
  • the yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out.
  • Embodiment 5 A method for preparing lithium hexafluorophosphate by dry method.
  • the method includes: 1) using a mesoporous silica plate with an opening rate of ⁇ 50% as a carrier, and the mesoporous silica plate porosity is 36 to 38%. , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top.
  • the air inlet is fed with phosphorus pentafluoride gas at 24 L/min for reaction, and the output
  • the gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine.
  • the remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.25 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride.
  • a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol.
  • the mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
  • the yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out.
  • Embodiment 6 Based on Embodiment 1, the material ratio, operating process and parameters are the same as those in Embodiment 1, with only the following differences: in step 2), between the phosphorus pentafluoride gas, preheat to 45 The pre-purge was carried out with nitrogen at °C for 2 minutes, and the nitrogen flow rate was 16 L/min. The remaining operating parameters are the same as those in Embodiment 1.
  • the yield calculation and purity test of the obtained lithium hexafluorophosphate were carried out.
  • the product yield reached 97.8%, which was slightly decreased, but the purity further increased to 99.95%, and the main component of the impurity was only lithium fluoride.
  • Embodiment 7 Based on Example 1, the material proportion, operating process and parameters are the same as Example 1, with the following differences: in step 2), between the introduction of phosphorus pentafluoride gas, preheating to 50 The pre-purge was carried out with nitrogen at °C for 2 minutes, and the nitrogen flow rate was 16 L/min. The remaining operating parameters are the same as those in Embodiment 1.
  • the yield calculation and purity test of the obtained lithium hexafluorophosphate were carried out.
  • the product yield reached 97.7%, which was slightly decreased, but the purity further increased to 99.96%, and the main component of the impurity was only lithium fluoride.
  • Example 1 Through the comparison of the above-mentioned Example 1, Example 6 and Example 7, it can be found that after the pre-purge, the yield of the product basically shows an extremely slight downward trend. But for product purity, there is a more obvious increase.
  • Research and analysis have found that during the deposition process of lithium fluoride, iodine vapor condenses in the carrier pores and acts as a binder to adhere and fix the lithium fluoride powder.
  • the lithium hexafluorophosphate produced by the original plan can basically meet the quality requirements of commercial lithium hexafluorophosphate HG/T4066-2008, but the quality of the lithium hexafluorophosphate obtained after nitrogen purging has reached the higher quality requirements of HG/T4066-2015, and can be directly used in one step.
  • the preparation of lithium hexafluorophosphate products that meet commercialization requirements does not require purification and other operations after preparation by conventional dry/wet methods, which has great promotion and implementation value.
  • the nitrogen purge temperature should be controlled at least between 45 and 55°C, and the optimal temperature should be controlled between 45 and 50°C.
  • Comparative Example 1 Based on Example 1, the material ratio, operating process and parameters are the same as Example 1, with the following differences: porous nickel-chromium alloy plates of equal specifications are used instead of mesoporous silica plates as carriers, porous The specific surface area and porosity of the nickel-chromium alloy plate are slightly higher than the mesoporous silica plate used in Example 1.
  • the yield calculation and purity test of the obtained lithium hexafluorophosphate were carried out.
  • the product yield reached 96.2%, which dropped slightly, while the purity dropped significantly to 91.72%, and the main impurities included lithium fluoride and iodine, as well as some metal diffusion components. .
  • the conversion of lithium fluoride into lithium hexafluorophosphate under the load of lithium fluoride and purging of phosphorus pentafluoride in Example 1 of the present invention is shown in Figure 1, which can achieve almost complete conversion and ends in step 1)
  • the temperature of the upper and lower sides of the mesoporous silica plate was measured.
  • the temperature of the lower side of the mesoporous silica plate in Example 1 reached about 49°C, so that iodine could not be effectively condensed and deposited.
  • the temperature of the upper side was basically the same as room temperature.

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Abstract

A method for preparing lithium hexafluorophosphate by a dry method, comprising: 1) taking foam glass as a carrier, placing the carrier in an open container, mixing lithium fluoride powder with iodine, then placing the mixture below the foam glass carrier, heating, and implementing the load of the lithium fluoride on the foam glass in an iodine evaporation mode to obtain a porous composite intermediate; and 2) placing the porous composite intermediate in a sealed reaction container, introducing a phosphorus pentafluoride gas to react to obtain a pre-product, placing the pre-product in an organic solvent for ultrasonic treatment, and collecting a bottom precipitate of the organic solvent to obtain lithium hexafluorophosphate.

Description

一种干法制备六氟磷酸锂的方法A kind of method for preparing lithium hexafluorophosphate by dry method 技术领域Technical field
本发明属于六氟磷酸锂的制备领域，尤其涉及一种干法制备六氟磷酸锂的方法。The invention belongs to the field of preparing lithium hexafluorophosphate, and in particular relates to a dry method for preparing lithium hexafluorophosphate.
背景技术Background technique
六氟磷酸锂（LiPF 6）是一种常见且常用的锂离子电池电解质锂盐，且经试验已证实是目前众多锂离子电池电解质锂盐中综合性能最优、使用效果最好的。为此，六氟磷酸锂的生产和制备始终是一个研究的热点。 Lithium hexafluorophosphate (LiPF 6 ) is a common and commonly used lithium salt for lithium-ion battery electrolytes, and tests have proven that it has the best overall performance and the best use effect among the many lithium-ion battery electrolyte lithium salts currently. For this reason, the production and preparation of lithium hexafluorophosphate has always been a research hotspot.
而干法制备是一种传统的制备六氟磷酸锂的方法，干法包括气固法和氟化氢溶剂法两种方法。气固法更为传统且简单，具有较高的生产效率，其直接将五氟化磷高温气体通入至存有氟化锂的密封容器中，于高温高压的条件下进行反应得到六氟磷酸锂产物，但该方法对氟化锂的转化率低，实际所得产物六氟磷酸锂中含有大量的氟化锂杂质，纯度低。而氟化氢溶剂法是将氟化锂置于无水氟化氢中进行多孔化，同时通入低流量的五氟化磷气体进行反应，该方法虽然克服了更为传统的气固法转化率低、产物纯度低的缺陷，但是该方案中利用无水氟化氢，其具有极强的挥发性和腐蚀性，具有较强的危害性，生产过程中存在较大的安全隐患，且反应全程需要保持低温进行，能耗大。Dry preparation is a traditional method for preparing lithium hexafluorophosphate. The dry method includes two methods: gas-solid method and hydrogen fluoride solvent method. The gas-solid method is more traditional and simple, with high production efficiency. It directly introduces high-temperature phosphorus pentafluoride gas into a sealed container containing lithium fluoride, and reacts under high temperature and high pressure to obtain the lithium hexafluorophosphate product. However, this method has a low conversion rate of lithium fluoride, and the actual product lithium hexafluorophosphate contains a large amount of lithium fluoride impurities and has low purity. The hydrogen fluoride solvent method places lithium fluoride in anhydrous hydrogen fluoride to make it porous, and at the same time introduces low-flow phosphorus pentafluoride gas for reaction. Although this method overcomes the low conversion rate and low product conversion rate of the more traditional gas-solid method. The disadvantage of low purity is that anhydrous hydrogen fluoride is used in this solution, which is extremely volatile and corrosive and highly harmful. There are major safety hazards in the production process, and the entire reaction needs to be carried out at low temperature. High energy consumption.
因此，对现有的方法制备方法进行改进，综合提高干法制备六氟磷酸锂的效果、效率以及安全性是十分有必要的。Therefore, it is very necessary to improve the existing preparation methods and comprehensively improve the effect, efficiency and safety of dry preparation of lithium hexafluorophosphate.
技术问题technical problem
为解决现有的干法制备六氟磷酸锂技术或存在转化率低、产品品质低下，或存在能耗高、安全隐患较大等问题，本发明提供了一种干法制备六氟磷酸锂的方法。In order to solve the problems that the existing dry method for preparing lithium hexafluorophosphate may have problems such as low conversion rate, low product quality, high energy consumption, and greater safety hazards, the present invention provides a method for dry preparation of lithium hexafluorophosphate.
本发明的目的在于：一、提高干法制备六氟磷酸锂的制备效率；二、提高所得六氟磷酸锂产物的纯度；三、避免使用氟化氢，提高制备的安全性。The objects of the present invention are: 1. to improve the preparation efficiency of lithium hexafluorophosphate prepared by dry method; 2. to improve the purity of the obtained lithium hexafluorophosphate product; 3. to avoid the use of hydrogen fluoride and improve the safety of preparation.
技术解决方案Technical solutions
为实现上述目的，本发明采用以下技术方案。In order to achieve the above objects, the present invention adopts the following technical solutions.
一种干法制备六氟磷酸锂的方法，所述方法包括：1）以泡沫玻璃为载体，于开放容器中，将氟化锂粉末与碘混合后置于泡沫玻璃载体下方，加热后采用碘蒸镀的方式实现氟化锂在泡沫玻璃上的负载，得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中，通入五氟化磷气体反应，实现氟化锂的转化后得到预产物，将预产物置于有机溶剂中超声处理，收集有机溶剂底部沉淀物即得到六氟磷酸锂。A method for preparing lithium hexafluorophosphate by dry method, the method includes: 1) using foam glass as a carrier, in an open container, mix lithium fluoride powder and iodine and place it under the foam glass carrier, and then use iodine evaporation after heating method to realize the loading of lithium fluoride on the foam glass to obtain a porous composite intermediate; 2) Place the porous composite intermediate in a sealed reaction vessel, introduce phosphorus pentafluoride gas to react, and achieve the conversion of lithium fluoride to obtain the pre-formed composite intermediate. The product is placed in an organic solvent for ultrasonic treatment, and the precipitate at the bottom of the organic solvent is collected to obtain lithium hexafluorophosphate.
在本发明技术方案中，综合了两种传统干法制备工艺的优点，具有工艺简洁、安全性高，且氟化锂转化率高、产物纯度高的优点。具体的，在本发明技术方案中，首先通过碘蒸镀的方式将氟化锂负载在具有均匀多孔结构的泡沫玻璃孔道中，同时碘接触到泡沫玻璃后遇冷冷凝作为胶黏剂实现对氟化锂的固定，避免流失氟化锂。而在后续的过程中，采用了传统气固法方案，控制五氟化磷气体流过多孔复合中间体，由于孔道结构的特性，使得五氟化磷气体与氟化锂具有更加充分的反应时间，实现氟化锂转化率的提高，同时氟化锂负载在孔道结构上，具有极大的比表面积，即实际具备更大的反应面积，能够更加有效且充分的反应，提高了反应效率。随后通过特定的有机溶剂选择，溶解去除碘同时确保六氟磷酸锂保持不溶的状态，通过超声的工艺实现载体和产物的分离。因此对于本发明技术方案而言，在整个反应过程中具有反应惰性且具备独特的结构特点的泡沫玻璃，与碘蒸镀是作为实现整个方案的核心。In the technical solution of the present invention, the advantages of two traditional dry preparation processes are combined, which has the advantages of simple process, high safety, high lithium fluoride conversion rate, and high product purity. Specifically, in the technical solution of the present invention, lithium fluoride is first loaded into the channels of foam glass with a uniform porous structure through iodine evaporation. At the same time, after the iodine comes into contact with the foam glass, it condenses when cold and acts as an adhesive to achieve fluorine removal. Fix lithium fluoride to avoid loss of lithium fluoride. In the subsequent process, a traditional gas-solid method was adopted to control the flow of phosphorus pentafluoride gas through the porous composite intermediate. Due to the characteristics of the pore structure, the phosphorus pentafluoride gas and lithium fluoride have a more sufficient reaction time. , to improve the conversion rate of lithium fluoride, and at the same time, lithium fluoride is loaded on the pore structure and has a huge specific surface area, that is, it actually has a larger reaction area, can react more effectively and fully, and improves the reaction efficiency. Then, specific organic solvents are selected to dissolve and remove iodine while ensuring that lithium hexafluorophosphate remains insoluble, and the carrier and product are separated through an ultrasonic process. Therefore, for the technical solution of the present invention, foam glass, which is reaction inert during the entire reaction process and has unique structural characteristics, and iodine evaporation are the core to realize the entire solution.
作为优选，步骤1）所述泡沫玻璃为开孔型泡沫二氧化硅，开孔率≥50 %；所述泡沫玻璃为板状和/或层片状，其设置在开放容器中用于对开放容器的开口进行封闭，使得碘蒸气流向泡沫玻璃。Preferably, the foam glass in step 1) is open-cell foamed silica, with an opening rate ≥ 50%; the foam glass is plate-shaped and/or lamellar-shaped, and is arranged in an open container for opening The opening of the container is closed, allowing the iodine vapor to flow toward the foam glass.
具体的，泡沫玻璃可采用介孔二氧化硅进行制备，介孔二氧化硅具有良好的反应惰性，不参与反应且具备丰富的多孔结构。以泡沫玻璃对开放容器的开口进行封闭，使其成为碘蒸气流动的必经路径，以实现氟化锂的稳定负载。同时，采用开放容器是为了形成稳定的气流，避免高压条件的产生，此外能够在无需降温的情况下保持泡沫玻璃处于相对较低的温度，有效实现对碘蒸气的冷凝。Specifically, foam glass can be prepared using mesoporous silica. Mesoporous silica has good reaction inertness, does not participate in reactions, and has a rich porous structure. The opening of the open container is closed with foam glass, making it a necessary path for the flow of iodine vapor to achieve a stable load of lithium fluoride. At the same time, the purpose of using an open container is to form a stable air flow and avoid the occurrence of high-pressure conditions. In addition, it can keep the foam glass at a relatively low temperature without cooling, and effectively achieve the condensation of iodine vapor.
另一方面，二氧化硅本身不具备十分优异的导热性，若采用多孔金属板或泡沫金属时，不但容易通过热扩散的方式引入杂质，更重要的是其自身热传递效率高，容易导致载体朝下一侧的面起到“负载面”的作用，因为其热量会快速地向外导出，致使下侧面温度始终保持较低，使得碘容易冷凝并“捕获”、“粘结”氟化锂粉体，而在面域中大量的粘附负载，会产生堆叠，导致其实际产物纯度产生剧烈的下降。On the other hand, silica itself does not have very excellent thermal conductivity. If porous metal plates or foam metals are used, not only is it easy to introduce impurities through thermal diffusion, but more importantly, its own heat transfer efficiency is high, which can easily lead to carrier The side facing downwards acts as a "loading surface" because its heat will be quickly exported outwards, causing the temperature of the lower side to always remain low, making it easy for iodine to condense and "capture" and "bond" lithium fluoride. Powders, and a large amount of adhesion load in the surface area will cause stacking, resulting in a drastic decrease in the actual product purity.
作为优选，步骤1）所述的氟化锂粉末目数≥200 目。Preferably, the mesh number of the lithium fluoride powder described in step 1) is ≥ 200 mesh.
氟化锂的目数过大会使得碘蒸气流无法有效带动氟化锂粉末运动。If the mesh number of lithium fluoride is too large, the iodine vapor flow will not be able to effectively drive the lithium fluoride powder.
作为优选，步骤1）所述氟化锂粉末与碘的质量比为1：（0.2～0.3）；所述泡沫玻璃的体积与氟化锂和碘的混合粉末松装体积比为1：（0.02～0.05）。Preferably, the mass ratio of the lithium fluoride powder and iodine in step 1) is 1: (0.2-0.3); the volume ratio of the foam glass to the bulk volume of the mixed powder of lithium fluoride and iodine is 1: (0.02 ~0.05).
控制上述的氟化锂与碘的质量比，确保能够产生足量的碘蒸气带动氟化锂粉末上升，但碘的用量不宜过大，以避免堵塞孔道或导致碘包裹在氟化锂外，导致降低氟化锂转化率或转化效率。此外，控制泡沫玻璃体积与粉体的松装体积比，是确保泡沫玻璃体积具有足够的内容空间以用于沉积氟化锂，此外由于泡沫玻璃实际也会产生一定的阻隔气体流通的作用，泡沫玻璃体积过大则会产生较大的气体交换阻碍，最终导致容器内侧/低侧（即相对于泡沫玻璃位置用于存置粉末的一侧）压力上升，导致蒸气压增大，无法有效实现碘的升华。Control the above-mentioned mass ratio of lithium fluoride and iodine to ensure that sufficient iodine vapor can be generated to drive the lithium fluoride powder to rise. However, the amount of iodine should not be too large to avoid blocking the pores or causing iodine to be wrapped outside the lithium fluoride, resulting in Reduce lithium fluoride conversion rate or conversion efficiency. In addition, controlling the ratio of the volume of the foam glass to the bulk volume of the powder is to ensure that the volume of the foam glass has enough content space for the deposition of lithium fluoride. In addition, because the foam glass actually has a certain effect of blocking gas circulation, the foam If the glass volume is too large, it will create a greater gas exchange obstruction, which will eventually cause the pressure on the inside/low side of the container (that is, the side used to store powder relative to the position of the foam glass) to increase, resulting in an increase in vapor pressure and inability to effectively achieve iodine release. sublimation.
作为优选，步骤1）所述加热控制加热温度为45～75 ℃。Preferably, the heating temperature in step 1) is controlled to be 45 to 75°C.
控制上述的加热温度能够有效稳定地产生碘蒸气气流，用于运载氟化锂同时实现胶黏作用。但实际操作过程中，应当控制温度≥55 ℃，以避免碘单质在载体下侧面产生大面积冷凝沉积。Controlling the above-mentioned heating temperature can effectively and stably generate an iodine vapor flow, which is used to carry lithium fluoride and achieve adhesion at the same time. However, during actual operation, the temperature should be controlled to be ≥55°C to avoid large-area condensation deposition of elemental iodine on the lower side of the carrier.
作为优选，步骤2）所述五氟化磷气体的流速控制在200～500 mL/min。Preferably, the flow rate of the phosphorus pentafluoride gas in step 2) is controlled at 200-500 mL/min.
控制上述的五氟化磷气体流速能够提高五氟化磷气体的利用率，并确保具有较高的反应效率。Controlling the above flow rate of phosphorus pentafluoride gas can improve the utilization rate of phosphorus pentafluoride gas and ensure high reaction efficiency.
作为优选，所述五氟化磷气体通入至密封反应容器中，其在进气端的相对一侧设置出气端，控制密封反应容器内压力维持1.15～1.25 atm。Preferably, the phosphorus pentafluoride gas is introduced into a sealed reaction vessel, which has a gas outlet end on the opposite side of the gas inlet end, and the pressure in the sealed reaction vessel is controlled to maintain 1.15-1.25 atm.
在该步骤中，通五氟化磷气体之间还可以通入预热至45～50 ℃的氮气进行预吹扫，通过预吹扫能够带走少量附着在氟化锂表面的微量碘单质，以避免其影响氟化锂与五氟化磷的接触反应，提高产物得率和纯度。此外，控制反应容器内的压力也是在于控制碘的升华，通过影响蒸气压等方式能够有效去除氟化锂表层的微量碘附着物同时避免全部的碘都被去除导致氟化锂在该过程中脱落流失。In this step, nitrogen gas preheated to 45-50°C can also be passed between the phosphorus pentafluoride gas for pre-purging. The pre-purging can take away a small amount of trace iodine elements attached to the surface of lithium fluoride. In order to avoid affecting the contact reaction between lithium fluoride and phosphorus pentafluoride, and improve the product yield and purity. In addition, controlling the pressure in the reaction vessel is also about controlling the sublimation of iodine. By affecting the vapor pressure and other methods, trace amounts of iodine attachments on the surface of lithium fluoride can be effectively removed while preventing all iodine from being removed and causing the lithium fluoride to fall off during the process. drain.
作为优选，步骤2）所述有机溶剂为醇。Preferably, the organic solvent in step 2) is alcohol.
醇能够有效溶解单质碘，实现产物和载体的分离，同时六氟磷酸锂不溶于醇，因此可以直接得到极高纯度的固体产物，无需进一步进行重结晶等操作，大大提高了生产制备的效率。Alcohol can effectively dissolve elemental iodine and achieve separation of the product and carrier. At the same time, lithium hexafluorophosphate is insoluble in alcohol. Therefore, extremely high-purity solid products can be obtained directly without further recrystallization and other operations, which greatly improves the efficiency of production and preparation.
有益效果beneficial effects
本发明的有益效果是：1）通过模板法配合具备了现有两种干法制备六氟磷酸锂的工艺的优点，同时有效克服了现有两种干法工艺的缺陷；2）整体工艺流程简介高效、具有极高的制备效率，所得的产物纯度能够达到99.5 %以上；3）方案绿色无污染，五氟化磷尾气方便回收并分离出微量碘蒸气后能够循环再利用，各个物料的回收利用率高；4）整体工艺安全，适宜推广大规模普及使用，且避免了氟化氢的使用，大大降低了成本。The beneficial effects of the present invention are: 1) The advantages of the existing two dry processes for preparing lithium hexafluorophosphate are combined with the template method, and at the same time it effectively overcomes the defects of the two existing dry processes; 2) The overall process flow is efficient, It has extremely high preparation efficiency, and the purity of the obtained product can reach more than 99.5%; 3) The solution is green and pollution-free. The phosphorus pentafluoride tail gas can be easily recovered and trace amounts of iodine vapor can be separated and recycled, and the recycling rate of each material is high. ; 4) The overall process is safe, suitable for large-scale popularization and use, and avoids the use of hydrogen fluoride, greatly reducing costs.
附图说明Description of the drawings
图1为本发明氟化锂负载以及向六氟磷酸锂转变的过程示意图；图2为对比例1中氟化锂负载以及向六氟磷酸锂转变的过程示意图。Figure 1 is a schematic diagram of the process of loading lithium fluoride and converting to lithium hexafluorophosphate in the present invention; Figure 2 is a schematic diagram of the process of loading lithium fluoride and converting to lithium hexafluorophosphate in Comparative Example 1.
本发明的实施方式Embodiments of the invention
以下结合具体实施例和说明书附图对本发明作出进一步清楚详细的描述说明。本领域普通技术人员在基于这些说明的情况下将能够实现本发明。此外，下述说明中涉及到的本发明的实施例通常仅是本发明一部分的实施例，而不是全部的实施例。因此，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都应当属于本发明保护的范围。The present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. A person of ordinary skill in the art will be able to implement the present invention based on these descriptions. In addition, the embodiments of the present invention mentioned in the following description are generally only some embodiments of the present invention, rather than all the embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts should fall within the scope of protection of the present invention.
在本发明的描述中，需要理解的是，术语“厚度”、“上”、“下”、“水平”、“顶”、“底”、“内”、“外”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定，“若干”的含义是表示一个或者多个。In the description of the present invention, it should be understood that the terms "thickness", "upper", "lower", "horizontal", "top", "bottom", "inner", "outer", "circumferential", etc. The indicated orientation or positional relationship is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description. It does not indicate or imply that the device or element referred to must have a specific orientation or a specific orientation. construction and operation, and therefore should not be construed as limitations of the invention. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise clearly and specifically limited, "several" means one or more.
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接或彼此可通讯；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系，除非另有明确的限定。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。In the present invention, unless otherwise clearly stated and limited, the terms "installation", "connection", "connection", "fixing" and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated; it can be mechanically connected, electrically connected or communicable with each other; it can be directly connected or indirectly connected through an intermediate medium; it can be the internal connection of two elements or the interaction between two elements, Unless otherwise expressly limited. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
如无特殊说明，本发明实施例所用原料均为市售或本领域技术人员可获得的原料；如无特殊说明，本发明实施例所用方法均为本领域技术人员所掌握的方法。Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or those available to those skilled in the art. Unless otherwise specified, the methods used in the examples of the present invention are all methods mastered by those skilled in the art.
实施例1:一种干法制备六氟磷酸锂的方法，所述方法包括：1）以开孔率≥50 %的介孔二氧化硅板为载体，介孔二氧化硅板孔隙率为36～38 %，板面积为2 m 2、厚度为0.15 m，设置于顶端开放的加热炉的顶部开口处，将200目的氟化锂粉末与碘粒以质量比1：0.25，共计12 dm 3的混合粉末混合后置于加热炉炉底，其中先均匀铺设碘粒在炉底、再均匀铺设氟化锂粉末，随后加热至65 ℃恒温保持至炉底不见粉体，即回收载体得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中部，其板面两侧一端设有进气口、一端设有出气口，进气口以16 L/min通入五氟化磷气体进行反应28 h，出气口连接尾气处理装置收集尾气并冷凝回收固态碘，其余尾气能够再次加热进入密封反应容器用于反应，且通过出气口的抽气速率控制密封反应容器内压力为1.2 atm，实现氟化锂的转化后得到负载有六氟磷酸锂的介孔二氧化硅板，将负载有六氟磷酸锂的介孔二氧化硅板置于乙醇中，负载有六氟磷酸锂的介孔二氧化硅板完全浸没在乙醇中之后进行超声处理，至无粉尘掉落后收集乙醇底部沉淀物，60 ℃低温即得到六氟磷酸锂。 Embodiment 1: A method for preparing lithium hexafluorophosphate by dry method, the method includes: 1) using a mesoporous silica plate with an opening rate of ≥50% as a carrier, and the mesoporous silica plate porosity is 36 to 38% , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.25, totaling 12 dm 3 Then it is placed at the bottom of the heating furnace, where iodine particles are first evenly spread on the bottom of the furnace, and then lithium fluoride powder is evenly spread, and then heated to 65°C and kept at a constant temperature until no powder is visible at the bottom of the furnace, that is, the carrier is recovered to obtain a porous composite intermediate; 2 ) Place the porous composite intermediate in the middle of the sealed reaction vessel, with an air inlet at one end and a gas outlet at one end on both sides of the plate. The air inlet is fed with phosphorus pentafluoride gas at 16 L/min for reaction for 28 hours. , the gas outlet is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine. The remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.2 atm through the pumping rate of the gas outlet to realize lithium fluoride. After the conversion, a mesoporous silica plate loaded with lithium hexafluorophosphate was obtained. The mesoporous silica plate loaded with lithium hexafluorophosphate was placed in ethanol. The mesoporous silica plate loaded with lithium hexafluorophosphate was completely immersed in ethanol and then subjected to ultrasonic treatment. , until no dust falls, collect the ethanol bottom precipitate, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产率达到98.1 %，产品六氟磷酸锂纯度约为99.61 %，杂质成分主要为氟化锂和碘。The yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out. The yield reached 98.1% and the purity of the product lithium hexafluorophosphate was approximately 99.61 %, the impurity components are mainly lithium fluoride and iodine.
实施例2：一种干法制备六氟磷酸锂的方法，所述方法包括：1）以开孔率≥50 %的介孔二氧化硅板为载体，介孔二氧化硅板孔隙率为36～38 %，板面积为2 m 2、厚度为0.15 m，设置于顶端开放的加热炉的顶部开口处，将200目的氟化锂粉末与碘粒以质量比1：0.2，共计6 dm 3的混合粉末混合后置于加热炉炉底，其中先均匀铺设碘粒在炉底、再均匀铺设氟化锂粉末，随后加热至55 ℃恒温保持至炉底不见粉体，即回收载体得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中部，其板面两侧一端设有进气口、一端设有出气口，进气口以10 L/min通入五氟化磷气体进行反应，出气口连接尾气处理装置收集尾气并冷凝回收固态碘，其余尾气能够再次加热进入密封反应容器用于反应，且通过出气口的抽气速率控制密封反应容器内压力为1.15 atm，实现氟化锂的转化后得到负载有六氟磷酸锂的介孔二氧化硅板，将负载有六氟磷酸锂的介孔二氧化硅板置于乙醇中，负载有六氟磷酸锂的介孔二氧化硅板完全浸没在乙醇中之后进行超声处理，至无粉尘掉落后收集乙醇底部沉淀物，60 ℃低温即得到六氟磷酸锂。 Embodiment 2: A method for preparing lithium hexafluorophosphate by dry method. The method includes: 1) using a mesoporous silica plate with an opening ratio of ≥50% as a carrier, and the mesoporous silica plate porosity is 36 to 38%. , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.2, totaling 6 dm 3. Then it is placed at the bottom of the heating furnace, where iodine particles are first evenly spread on the bottom of the furnace, and then lithium fluoride powder is evenly spread, and then heated to 55°C and kept at a constant temperature until no powder is visible at the bottom of the furnace, that is, the carrier is recovered to obtain a porous composite intermediate; 2 ) Place the porous composite intermediate in the middle of the sealed reaction vessel, with an air inlet at one end and a gas outlet at one end on both sides of the plate. The air inlet is fed with phosphorus pentafluoride gas at 10 L/min for reaction, and the output The gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine. The remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.15 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride. Finally, a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained. The mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol. The mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产率达到99.0 %，产品六氟磷酸锂纯度约为99.81 %，杂质成分主要为氟化锂和碘。The yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out. The yield reached 99.0% and the purity of the product lithium hexafluorophosphate was approximately 99.81 %, the impurity components are mainly lithium fluoride and iodine.
实施例3:一种干法制备六氟磷酸锂的方法，所述方法包括：1）以开孔率≥50 %的介孔二氧化硅板为载体，介孔二氧化硅板孔隙率为36～38 %，板面积为2 m 2、厚度为0.15 m，设置于顶端开放的加热炉的顶部开口处，将200目的氟化锂粉末与碘粒以质量比1：0.3，共计15 dm 3的混合粉末混合后置于加热炉炉底，其中先均匀铺设碘粒在炉底、再均匀铺设氟化锂粉末，随后加热至75 ℃恒温保持至炉底不见粉体，即回收载体得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中部，其板面两侧一端设有进气口、一端设有出气口，进气口以24 L/min通入五氟化磷气体进行反应，出气口连接尾气处理装置收集尾气并冷凝回收固态碘，其余尾气能够再次加热进入密封反应容器用于反应，且通过出气口的抽气速率控制密封反应容器内压力为1.25 atm，实现氟化锂的转化后得到负载有六氟磷酸锂的介孔二氧化硅板，将负载有六氟磷酸锂的介孔二氧化硅板置于乙醇中，负载有六氟磷酸锂的介孔二氧化硅板完全浸没在乙醇中之后进行超声处理，至无粉尘掉落后收集乙醇底部沉淀物，60 ℃低温即得到六氟磷酸锂。 Embodiment 3: A method for preparing lithium hexafluorophosphate by dry method, the method includes: 1) using a mesoporous silica plate with an opening rate of ≥50% as a carrier, and the mesoporous silica plate porosity is 36 to 38% , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.3, totaling 15 dm 3 . Then it is placed at the bottom of the heating furnace, where iodine particles are evenly laid on the bottom of the furnace, and then lithium fluoride powder is evenly laid, and then heated to 75°C and kept at a constant temperature until no powder is visible at the bottom of the furnace, that is, the carrier is recovered to obtain a porous composite intermediate; 2 ) Place the porous composite intermediate in the middle of the sealed reaction vessel, with an air inlet at one end and a gas outlet at one end on both sides of the plate. The air inlet is fed with phosphorus pentafluoride gas at 24 L/min for reaction, and the output The gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine. The remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.25 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride. Finally, a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained. The mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol. The mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产率达到97.9 %，产品六氟磷酸锂纯度约为99.54 %，杂质成分主要为氟化锂和碘。The yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out. The yield reached 97.9% and the purity of the product lithium hexafluorophosphate was approximately 99.54 %, the impurity components are mainly lithium fluoride and iodine.
实施例4:一种干法制备六氟磷酸锂的方法，所述方法包括：1）以开孔率≥50 %的介孔二氧化硅板为载体，介孔二氧化硅板孔隙率为36～38 %，板面积为2 m 2、厚度为0.15 m，设置于顶端开放的加热炉的顶部开口处，将200目的氟化锂粉末与碘粒以质量比1：0.25，共计12 dm 3的混合粉末混合后置于加热炉炉底，其中先均匀铺设碘粒在炉底、再均匀铺设氟化锂粉末，随后加热至65 ℃恒温保持至炉底不见粉体，即回收载体得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中部，其板面两侧一端设有进气口、一端设有出气口，进气口以12 L/min通入五氟化磷气体进行反应，出气口连接尾气处理装置收集尾气并冷凝回收固态碘，其余尾气能够再次加热进入密封反应容器用于反应，且通过出气口的抽气速率控制密封反应容器内压力为1.15 atm，实现氟化锂的转化后得到负载有六氟磷酸锂的介孔二氧化硅板，将负载有六氟磷酸锂的介孔二氧化硅板置于乙醇中，负载有六氟磷酸锂的介孔二氧化硅板完全浸没在乙醇中之后进行超声处理，至无粉尘掉落后收集乙醇底部沉淀物，60 ℃低温即得到六氟磷酸锂。 Embodiment 4: A method for preparing lithium hexafluorophosphate by dry method. The method includes: 1) using a mesoporous silica plate with an opening rate of ≥50% as a carrier, and the mesoporous silica plate porosity is 36 to 38%. , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.25, totaling 12 dm 3 Then it is placed at the bottom of the heating furnace, where iodine particles are first evenly spread on the bottom of the furnace, and then lithium fluoride powder is evenly spread, and then heated to 65°C and kept at a constant temperature until no powder is visible at the bottom of the furnace, that is, the carrier is recovered to obtain a porous composite intermediate; 2 ) Place the porous composite intermediate in the middle of the sealed reaction vessel, with an air inlet on one end and a gas outlet on both sides of the plate. The air inlet is fed with phosphorus pentafluoride gas at 12 L/min for reaction, and the output The gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine. The remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.15 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride. Finally, a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained. The mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol. The mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产率达到98.3 %，产品六氟磷酸锂纯度约为99.75 %，杂质成分主要为氟化锂和碘。The yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out. The yield reached 98.3% and the purity of the product lithium hexafluorophosphate was approximately 99.75 %, the impurity components are mainly lithium fluoride and iodine.
实施例5:一种干法制备六氟磷酸锂的方法，所述方法包括：1）以开孔率≥50 %的介孔二氧化硅板为载体，介孔二氧化硅板孔隙率为36～38 %，板面积为2 m 2、厚度为0.15 m，设置于顶端开放的加热炉的顶部开口处，将200目的氟化锂粉末与碘粒以质量比1：0.25，共计12 dm 3的混合粉末混合后置于加热炉炉底，其中先均匀铺设碘粒在炉底、再均匀铺设氟化锂粉末，随后加热至65 ℃恒温保持至炉底不见粉体，即回收载体得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中部，其板面两侧一端设有进气口、一端设有出气口，进气口以24 L/min通入五氟化磷气体进行反应，出气口连接尾气处理装置收集尾气并冷凝回收固态碘，其余尾气能够再次加热进入密封反应容器用于反应，且通过出气口的抽气速率控制密封反应容器内压力为1.25 atm，实现氟化锂的转化后得到负载有六氟磷酸锂的介孔二氧化硅板，将负载有六氟磷酸锂的介孔二氧化硅板置于乙醇中，负载有六氟磷酸锂的介孔二氧化硅板完全浸没在乙醇中之后进行超声处理，至无粉尘掉落后收集乙醇底部沉淀物，60 ℃低温即得到六氟磷酸锂。 Embodiment 5: A method for preparing lithium hexafluorophosphate by dry method. The method includes: 1) using a mesoporous silica plate with an opening rate of ≥50% as a carrier, and the mesoporous silica plate porosity is 36 to 38%. , the plate area is 2 m 2 and the thickness is 0.15 m. It is set at the top opening of the heating furnace with an open top. Mix 200 mesh lithium fluoride powder and iodine particles at a mass ratio of 1:0.25, totaling 12 dm 3 Then it is placed at the bottom of the heating furnace, where iodine particles are first evenly spread on the bottom of the furnace, and then lithium fluoride powder is evenly spread, and then heated to 65°C and kept at a constant temperature until no powder is visible at the bottom of the furnace, that is, the carrier is recovered to obtain a porous composite intermediate; 2 ) Place the porous composite intermediate in the middle of the sealed reaction vessel, with an air inlet at one end and a gas outlet at one end on both sides of the plate. The air inlet is fed with phosphorus pentafluoride gas at 24 L/min for reaction, and the output The gas port is connected to the tail gas treatment device to collect the tail gas and condense it to recover solid iodine. The remaining tail gas can be reheated and entered into the sealed reaction vessel for reaction, and the pressure in the sealed reaction vessel is controlled to 1.25 atm through the exhaust rate of the gas outlet to realize the conversion of lithium fluoride. Finally, a mesoporous silica plate loaded with lithium hexafluorophosphate is obtained. The mesoporous silica plate loaded with lithium hexafluorophosphate is placed in ethanol. The mesoporous silica plate loaded with lithium hexafluorophosphate is completely immersed in ethanol and then subjected to ultrasonic treatment until Collect the ethanol bottom precipitate after no dust falls, and obtain lithium hexafluorophosphate at a low temperature of 60°C.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产率达到98.2 %，产品六氟磷酸锂纯度约为99.58 %，杂质成分主要为氟化锂和碘。The yield calculation and purity testing of the obtained lithium hexafluorophosphate were carried out. The yield reached 98.2% and the purity of the product lithium hexafluorophosphate was approximately 99.58 %, the impurity components are mainly lithium fluoride and iodine.
实施例6:基于实施例1的，物料配比、操作过程和参数均与实施例1相同，仅有以下不同：步骤2）中在通入五氟化磷气体之间通入预热至45 ℃的氮气进行持续2 min的预吹扫，氮气流速为16 L/min。其余操作参数等均与实施例1相同。Embodiment 6: Based on Embodiment 1, the material ratio, operating process and parameters are the same as those in Embodiment 1, with only the following differences: in step 2), between the phosphorus pentafluoride gas, preheat to 45 The pre-purge was carried out with nitrogen at ℃ for 2 minutes, and the nitrogen flow rate was 16 L/min. The remaining operating parameters are the same as those in Embodiment 1.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产物得率达到97.8 %，略微有所下降，但纯度进一步上升到99.95 %，且杂质主要成分仅为氟化锂。The yield calculation and purity test of the obtained lithium hexafluorophosphate were carried out. The product yield reached 97.8%, which was slightly decreased, but the purity further increased to 99.95%, and the main component of the impurity was only lithium fluoride.
实施例7:基于实施例1的，物料配比、操作过程和参数均与实施例1相同，仅有以下不同：步骤2）中在通入五氟化磷气体之间通入预热至50 ℃的氮气进行持续2 min的预吹扫，氮气流速为16 L/min。其余操作参数等均与实施例1相同。Embodiment 7: Based on Example 1, the material proportion, operating process and parameters are the same as Example 1, with the following differences: in step 2), between the introduction of phosphorus pentafluoride gas, preheating to 50 The pre-purge was carried out with nitrogen at ℃ for 2 minutes, and the nitrogen flow rate was 16 L/min. The remaining operating parameters are the same as those in Embodiment 1.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产物得率达到97.7 %，略微有所下降，但纯度进一步上升到99.96 %，且杂质主要成分仅为氟化锂。The yield calculation and purity test of the obtained lithium hexafluorophosphate were carried out. The product yield reached 97.7%, which was slightly decreased, but the purity further increased to 99.96%, and the main component of the impurity was only lithium fluoride.
通过上述实施例1、实施例6和实施例7的对比可以发现，在经过但其预吹扫后，产品的得率基本呈现一个极其微小的下降趋势。但对于产品纯度而言，有一个较为明显的上升。经研究分析发现，在氟化锂的沉积过程中，碘蒸气遇冷凝结在载体孔中并作为粘结剂粘附固定氟化锂粉末，但同样的，在该过程中，会有极其微量的碘冷凝在氟化锂的外表面而非氟化锂与载体之间的界限处，并且在后续的氟化锂与五氟化磷反应转化过程中，被“包覆”在其中，只是这部分极微量的碘无法在后面的超声处理中洗去，影响了产品纯度。而通过热氮气的预吹扫，能够保障产品得率的同时，实现了六氟磷酸锂的高度纯化。原方案所制得的六氟磷酸锂基本能够满足对于商品化六氟磷酸锂HG/T4066-2008的品质要求，但经过氮气吹扫后所得的六氟磷酸锂品质达到了更高的HG/T4066-2015的品质要求，能够一步直接制备得到满足商品化要求的六氟磷酸锂产品，而不需要如常规干/湿法等方法制备后还需要进行纯化等操作，具备极大的推广和实施价值。Through the comparison of the above-mentioned Example 1, Example 6 and Example 7, it can be found that after the pre-purge, the yield of the product basically shows an extremely slight downward trend. But for product purity, there is a more obvious increase. Research and analysis have found that during the deposition process of lithium fluoride, iodine vapor condenses in the carrier pores and acts as a binder to adhere and fix the lithium fluoride powder. However, in the same process, there will be extremely trace amounts of Iodine is condensed on the outer surface of lithium fluoride rather than at the boundary between lithium fluoride and the carrier, and is "coated" in it during the subsequent reaction and conversion of lithium fluoride and phosphorus pentafluoride, but this part A very small amount of iodine cannot be washed away in the subsequent ultrasonic treatment, affecting the purity of the product. Pre-purging with hot nitrogen gas can ensure product yield and achieve a high degree of purification of lithium hexafluorophosphate. The lithium hexafluorophosphate produced by the original plan can basically meet the quality requirements of commercial lithium hexafluorophosphate HG/T4066-2008, but the quality of the lithium hexafluorophosphate obtained after nitrogen purging has reached the higher quality requirements of HG/T4066-2015, and can be directly used in one step. The preparation of lithium hexafluorophosphate products that meet commercialization requirements does not require purification and other operations after preparation by conventional dry/wet methods, which has great promotion and implementation value.
但是，需要注意的是，不应当采用更高的温度进行吹扫。这是因为更高温度的吹扫容易导致部分作为“粘结剂”的碘被带走，导致产品的得率逐渐下降。因此为控制得率和产品品质，应当至少控制氮气的吹扫温度于45～55 ℃之间，且最优应当控制在45～50 ℃之间。However, it should be noted that higher temperatures should not be used for purging. This is because purging at higher temperatures can easily cause part of the iodine used as a "binder" to be taken away, resulting in a gradual decrease in product yield. Therefore, in order to control the yield and product quality, the nitrogen purge temperature should be controlled at least between 45 and 55°C, and the optimal temperature should be controlled between 45 and 50°C.
对比例1:基于实施例1的，物料配比、操作过程和参数均与实施例1相同，仅有以下不同：以等规格的多孔镍铬合金板替代介孔二氧化硅板作为载体，多孔镍铬合金板比表面积和孔隙率均略高于实施例1所用介孔二氧化硅板。Comparative Example 1: Based on Example 1, the material ratio, operating process and parameters are the same as Example 1, with the following differences: porous nickel-chromium alloy plates of equal specifications are used instead of mesoporous silica plates as carriers, porous The specific surface area and porosity of the nickel-chromium alloy plate are slightly higher than the mesoporous silica plate used in Example 1.
对所得的六氟磷酸锂进行产率计算和纯度检测，经检测产物得率达到96.2 %，有所下降，而纯度发生显著下降至91.72 %，且杂质主要成分包括氟化锂和碘，以及部分金属扩散成分。The yield calculation and purity test of the obtained lithium hexafluorophosphate were carried out. The product yield reached 96.2%, which dropped slightly, while the purity dropped significantly to 91.72%, and the main impurities included lithium fluoride and iodine, as well as some metal diffusion components. .
如图1和图2所示，本发明实施例1的氟化锂负载以及五氟化磷吹扫下向六氟磷酸锂的转变如图1所示，其能够几乎完全实现转化，且在步骤1）结束后立刻对介孔二氧化硅板上下面进行温度检测，实施例1中介孔二氧化硅板下侧面温度达到约49 ℃，使得碘无法有效凝结沉积，上侧面温度与室温基本相当，而对比例1中的多孔镍铬合金板下侧面沉积有大量的碘单质且该部分温度仅略高于室温，约为38～41 ℃，能够满足碘继续沉积的需求。As shown in Figure 1 and Figure 2, the conversion of lithium fluoride into lithium hexafluorophosphate under the load of lithium fluoride and purging of phosphorus pentafluoride in Example 1 of the present invention is shown in Figure 1, which can achieve almost complete conversion and ends in step 1) Immediately after that, the temperature of the upper and lower sides of the mesoporous silica plate was measured. The temperature of the lower side of the mesoporous silica plate in Example 1 reached about 49°C, so that iodine could not be effectively condensed and deposited. The temperature of the upper side was basically the same as room temperature. In the comparative example A large amount of elemental iodine is deposited on the lower side of the porous nickel-chromium alloy plate in 1 and the temperature of this part is only slightly higher than room temperature, about 38-41°C, which can meet the demand for continued deposition of iodine.
该温度的差异性导致采用多孔镍铬合金板等多孔金属载体时，部分氟化锂颗粒在载体的下侧面被碘单质粘附固定并被大量包覆，导致其无法有效实现反应转变，导致最终所得产物的纯度显著下降。This temperature difference causes that when porous metal carriers such as porous nickel-chromium alloy plates are used, some lithium fluoride particles are adhered and fixed by iodine elements on the lower side of the carrier and are heavily coated, resulting in the inability to effectively realize the reaction transformation, resulting in the final The purity of the product obtained decreased significantly.
因此，对于本发明技术方案而言，选择载体时除了需要考虑载体的孔隙率等结构特征以及需要其具备反应惰性等化学性质以外，还需要进一步综合考量其导热性等方面物理特性。经过大量的试验，泡沫二氧化硅、尤其是开孔型介孔二氧化硅板是最优的选择。Therefore, for the technical solution of the present invention, in addition to the structural characteristics such as porosity and chemical properties such as reaction inertness of the carrier, when selecting a carrier, it is also necessary to further comprehensively consider its physical properties such as thermal conductivity. After a lot of experiments, foamed silica, especially open-cell mesoporous silica plates, is the best choice.

Claims (8)

  1. 一种干法制备六氟磷酸锂的方法，其特征在于，所述方法包括：1）以泡沫玻璃为载体，于开放容器中，将氟化锂粉末与碘混合后置于泡沫玻璃载体下方，加热后采用碘蒸镀的方式实现氟化锂在泡沫玻璃上的负载，得到多孔复合中间体；2）将多孔复合中间体置于密封反应容器中，通入五氟化磷气体反应，实现氟化锂的转化后得到预产物，将预产物置于有机溶剂中超声处理，收集有机溶剂底部沉淀物即得到六氟磷酸锂。A method for preparing lithium hexafluorophosphate by dry method, characterized in that the method includes: 1) using foam glass as a carrier, in an open container, mix lithium fluoride powder and iodine and place it under the foam glass carrier, and then use The method of iodine evaporation realizes the loading of lithium fluoride on the foam glass to obtain a porous composite intermediate; 2) Place the porous composite intermediate in a sealed reaction vessel, and introduce phosphorus pentafluoride gas to react to achieve the reaction of lithium fluoride. After conversion, a pre-product is obtained. The pre-product is placed in an organic solvent for ultrasonic treatment, and the precipitate at the bottom of the organic solvent is collected to obtain lithium hexafluorophosphate.
  2. 根据权利要求1所述的一种干法制备六氟磷酸锂的方法，其特征在于，步骤1）所述泡沫玻璃为开孔型泡沫二氧化硅，开孔率≥50 %；所述泡沫玻璃为板状和/或层片状，其设置在开放容器中用于对开放容器的开口进行封闭，使得碘蒸气流向泡沫玻璃。A method for preparing lithium hexafluorophosphate by dry method according to claim 1, characterized in that, in step 1), the foamed glass is open-pore foamed silica, with an opening rate ≥ 50%; the foamed glass is plate-shaped And/or in the form of sheets, which are arranged in an open container for closing the opening of the open container so that the iodine vapor flows to the foam glass.
  3. 根据权利要求1所述的一种干法制备六氟磷酸锂的方法，其特征在于，步骤1）所述的氟化锂粉末目数≥200 目。A method for preparing lithium hexafluorophosphate by dry method according to claim 1, characterized in that the mesh number of the lithium fluoride powder in step 1) is ≥ 200 mesh.
  4. 根据权利要求1或3所述的一种干法制备六氟磷酸锂的方法，其特征在于，步骤1）所述氟化锂粉末与碘的质量比为1：（0.2～0.3）；所述泡沫玻璃的体积与氟化锂和碘的混合粉末松装体积比为1：（0.02～0.05）。A method for preparing lithium hexafluorophosphate by dry method according to claim 1 or 3, characterized in that the mass ratio of the lithium fluoride powder and iodine in step 1) is 1: (0.2~0.3); the mass ratio of the foam glass The bulk volume ratio of the mixed powder of lithium fluoride and iodine is 1: (0.02~0.05).
  5. 根据权利要求4所述的一种干法制备六氟磷酸锂的方法，其特征在于，步骤1）所述加热控制加热温度为45～75 ℃。A method for preparing lithium hexafluorophosphate by dry method according to claim 4, characterized in that the heating temperature in step 1) is controlled to be 45-75°C.
  6. 根据权利要求1所述的一种干法制备六氟磷酸锂的方法，其特征在于，步骤2）所述五氟化磷气体的流速针对每平方米板面面积控制在5～12 L/min。A method for preparing lithium hexafluorophosphate by dry method according to claim 1, characterized in that the flow rate of the phosphorus pentafluoride gas in step 2) is controlled at 5 to 12 L/min per square meter of plate area.
  7. 根据权利要求1或6所述的一种干法制备六氟磷酸锂的方法，其特征在于，所述五氟化磷气体通入至密封反应容器中，其在进气端的相对一侧设置出气端，控制密封反应容器内压力维持1.15～1.25 atm。A method for preparing lithium hexafluorophosphate by dry method according to claim 1 or 6, characterized in that the phosphorus pentafluoride gas is introduced into a sealed reaction vessel, which has a gas outlet end on the opposite side of the gas inlet end, and controls The pressure in the sealed reaction vessel is maintained at 1.15~1.25 atm.
  8. 根据权利要求1所述的一种干法制备六氟磷酸锂的方法，其特征在于，步骤2）所述有机溶剂为醇。A method for preparing lithium hexafluorophosphate by dry method according to claim 1, characterized in that the organic solvent in step 2) is alcohol.
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