WO2025143183A1 - Procédé de production de pentafluorure de phosphore et procédé de production d'hexafluorophosphate - Google Patents

Procédé de production de pentafluorure de phosphore et procédé de production d'hexafluorophosphate Download PDF

Info

Publication number
WO2025143183A1
WO2025143183A1 PCT/JP2024/046305 JP2024046305W WO2025143183A1 WO 2025143183 A1 WO2025143183 A1 WO 2025143183A1 JP 2024046305 W JP2024046305 W JP 2024046305W WO 2025143183 A1 WO2025143183 A1 WO 2025143183A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfuric acid
hydrogen fluoride
phosphorus pentafluoride
mass
phosphorus
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.)
Pending
Application number
PCT/JP2024/046305
Other languages
English (en)
Japanese (ja)
Inventor
公祐 佐野
弘幹 濱口
宣久 木村
晃典 原田
哲平 大田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanto Denka Kogyo Co Ltd
Original Assignee
Kanto Denka Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kanto Denka Kogyo Co Ltd filed Critical Kanto Denka Kogyo Co Ltd
Publication of WO2025143183A1 publication Critical patent/WO2025143183A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/10—Halides or oxyhalides of phosphorus

Definitions

  • the present invention relates to a method for producing phosphorus pentafluoride and a method for producing hexafluorophosphate.
  • Phosphorus pentafluoride is industrially useful and important in the fields of semiconductor materials and battery materials.
  • it is used as a raw material for lithium hexafluorophosphate, which is used as an electrolyte for lithium ion batteries and as a catalyst for organic synthesis.
  • Patent Document 5 describes a method for generating phosphorus pentafluoride from hexafluorophosphoric acid hydrate using sulfur trioxide, oleum, or fluorosulfonic acid.
  • HPF6 ⁇ nH2O + SO3 (fuming sulfuric acid) ⁇ PF5 + nH2SO4 (Patent Document 5 )
  • Patent Documents 1 and 2 generate 5 equivalents of by-product HCl.
  • the boiling point of HCl is -84.9°C, which is very close to the boiling point of phosphorus pentafluoride, which is -84.8°C, making separation by distillation difficult and industrially disadvantageous.
  • Patent Document 3 The method described in Patent Document 3 is difficult to control because of an explosive reaction involving the oxidation of zero-valent phosphorus, and since F2 is very expensive, this method is economically disadvantageous.
  • Patent Document 4 The method described in Patent Document 4 is unsuitable for industrialization because the reaction itself has a low yield of about 12% and produces a large amount of calcium sulfate as a by-product.
  • the amount of sulfuric acid is 4 moles or more per mole of phosphorus element of the phosphorus component during the dehydration step, not only because it improves the production efficiency of phosphorus pentafluoride, but also because, when a concentration step described later is performed, the amount of heat required for the concentration step can be reduced due to the already high concentration of sulfuric acid used for concentration.
  • the amount of sulfuric acid is 20 moles or less per mole of phosphorus element of the phosphorus component during the dehydration step in terms of boiler efficiency, and more preferably 15 moles or less.
  • the dehydration step is not particularly limited by the pressure at which it is carried out, but is preferably carried out under reduced pressure, as this effectively accelerates the rate at which phosphorus pentafluoride is produced.
  • the pressure in the dehydration step is preferably -0.07 to 0.10 MPaG. More preferably, it is -0.05 to 0.05 MPaG, and most preferably, it is -0.03 to 0.01 MPaG.
  • it is preferably -0.07 to -0.01 MPaG, and more preferably, it is -0.05 to -0.01 MPaG.
  • step c) may be included before the step a).
  • step c) Step of recovering hydrogen fluoride that has been subjected to the dehydration step
  • an example of a method for recovering hydrogen fluoride in step c) is a method in which hydrogen fluoride is distilled from the reaction system by heating in the presence of sulfuric acid during or after the dehydration step, and then recovered using a cooling trap or the like.
  • the cooling temperature of the cooling water or the like is, for example, preferably ⁇ 60 to 20° C., more preferably ⁇ 40 to 10° C., and further preferably ⁇ 20 to 0° C.
  • hydrogen fluoride can be recovered from the reaction vessel during or after the dehydration step and reused, and sulfuric acid of higher purity can be easily obtained.
  • the hydrolysis of unreacted hexafluorophosphoric acid, difluorophosphoric acid which is a hydrolyzate of hexafluorophosphoric acid, and monofluorophosphoric acid which has been further hydrolyzed proceeds from about 100° C. From the viewpoint of promoting the hydrolysis and recovering high-purity hydrogen fluoride and sulfuric acid, it is preferable to heat the inside of the reaction vessel at 100° C. or higher in the step c). On the other hand, from the viewpoint of suppressing the progress of concentration of sulfuric acid and an increase in the water content in the hydrogen fluoride distilled off, it is preferable to heat at 250° C. or lower.
  • the distillation of hydrogen fluoride from the post-reaction liquid may be promoted by bubbling with an inert gas.
  • the reaction may be carried out under reduced pressure conditions. As shown in Example 1 described later, it is possible to make the bottom residue after this step c ) substantially free of impurities other than orthophosphoric acid, sulfuric acid, and water.
  • the chemical formula for hydrolysis of H2PO3F and HPO2F2 is as follows: HPO 2 F 2 +2H 2 O ⁇ H 3 PO 4 +2HF H2PO3F + H2O ⁇ H3PO4 + HF
  • H2PO3F H2O ⁇ H3PO4 + HF
  • the fluorine ion concentration in the reaction solution after step c) is preferably 1000 ppm by mass or less because recovery efficiency is high, and more preferably 100 ppm by mass or less.
  • the fluorine ion concentration can be measured by ion chromatography.
  • the method for concentrating sulfuric acid is not particularly limited, and a known method can be used.
  • general concentration by vacuum reduced pressure concentration, electrolysis, or electrodialysis may be used.
  • the absolute pressure in the reduced pressure reaction vessel is preferably in the range of 1 to 100 hPa, more preferably in the range of 1 to 20 hPa.
  • the heating temperature in the step of concentrating sulfuric acid is preferably 150°C or higher, more preferably 200°C or higher. It is also preferably 300°C or lower, more preferably 250°C or lower. The range is preferably 150 to 300°C, more preferably 200 to 250°C.
  • the concentration of sulfuric acid after concentration is preferably 80% by mass or more. If the concentration is this or more, sufficient dehydration from hexafluorophosphoric acid hydrate proceeds in the step of reusing the concentrated sulfuric acid in the production of phosphorus pentafluoride, and a decrease in the yield of phosphorus pentafluoride can be suppressed. 90% by mass or more is more preferable, and 97% by mass or more is particularly preferable.
  • the upper limit of the sulfuric acid concentration after concentration is 100% by mass, and 99% by mass or less is preferable in terms of reducing the energy required for concentration.
  • the concentration of sulfuric acid before concentration is preferably 75% by mass or more, and more preferably 90% by mass or more, from the viewpoint of successfully obtaining a high concentration of sulfuric acid by the concentration in step a).
  • the concentration of sulfuric acid before concentration is preferably, for example, 98% by mass or less, from the viewpoint of ease of production.
  • phosphoric acid which is the raw material for hexafluorophosphoric acid hydrate
  • phosphoric acid which is the raw material for hexafluorophosphoric acid hydrate
  • the lower the water content of phosphoric acid the higher the viscosity becomes, which reduces the stirring and heating efficiency and makes concentration difficult. Therefore, mixing phosphoric acid and sulfuric acid and concentrating them is also preferable in this respect.
  • the obtained sulfuric acid can be used again in the dehydration process to dehydrate new hexafluorophosphoric acid hydrate, thereby avoiding the generation of sulfuric acid waste.
  • the method for producing a hexafluorophosphate salt in this embodiment includes a step of reacting the phosphorus pentafluoride produced by the above-mentioned method with a fluoride salt in an organic solvent or a hydrogen fluoride solvent according to the following formula (1).
  • M is one or more selected from the group consisting of Li, Na, K, Rb, Cs, Ag, and NH4 .
  • the organic solvent used in the process for producing the hexafluorophosphate salt is preferably a non-aqueous solvent such as an ether or a carbonate.
  • a non-aqueous solvent such as an ether or a carbonate.
  • ethers and carbonates examples include ethyl carbonate, dipentyl carbonate, methylheptyl carbonate, ethylheptyl carbonate, diheptyl carbonate, methylhexyl carbonate, ethylhexyl carbonate, dihexyl carbonate, methyloctyl carbonate, ethyloctyl carbonate, dioctyl carbonate, methyltrifluoroethyl carbonate, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, and 2,3-pentylene carbonate. Since the resulting reaction solution can be used as an electrolyte as it is, it is more preferable to select from dimethyl carbonate (DMC) and ethylene carbonate. Two or more of these ethers and carbonates may be mixed and used.
  • DMC dimethyl carbonate
  • the reaction temperature in the process for producing the hexafluorophosphate is preferably -20°C to 100°C. If it is -20°C or higher, it is possible to prevent adverse effects on stirring due to an increase in the viscosity of the solvent. If it is 100°C or lower, it is possible to suppress the decomposition of the hexafluorophosphate and the solvent, and the progress of the evaporation of the solvent.
  • the reaction temperature is more preferably 0°C to 50°C, and even more preferably 10°C to 30°C.
  • the reaction time in the process for producing the hexafluorophosphate salt is not particularly limited because the reaction between phosphorus pentafluoride and the fluoride salt is very fast, and depends on the introduction rate of phosphorus pentafluoride.
  • M in formula (1) is preferably one selected from Li, Na, K, Rb, Cs, Ag, and NH4 , as it is in high demand as a battery material, a catalyst for organic synthesis, and the like, and has a high availability, and is particularly preferably one selected from Li, Na, and K, and is most preferably Li.
  • the collected liquid was circulated in the device for 3 hours, resulting in 0.57 mol (yield 40%) of lithium hexafluorophosphate.
  • the production rate of lithium hexafluorophosphate at this time was 29 g/hour.
  • the mixture was circulated in the device for 11 hours, resulting in 1.24 mol (yield 86%) of lithium hexafluorophosphate.
  • Example 5 Concentration of a mixed solution of 85% by weight phosphoric acid and 98% by weight sulfuric acid 900.1 g (7.81 mol, water: 7.50 mol) of 85% by weight phosphoric acid and 3949.7 g (39.46 mol, water: 4.39 mol) of 98% by weight sulfuric acid were transferred to a 5 L glass three-neck flask, reduced to 6 hPa with a diaphragm pump, and heated in an oil bath at an internal temperature of 200 ° C. for 7 hours. The moisture concentration of the residue was reduced to 1% by weight or less when measured with a Karl Fischer moisture meter.
  • Second step 6533 g of a mixed solution (containing 1167 g, 11.9 mol of phosphoric acid, 5287 g, 54.0 mol of sulfuric acid, and 79 g, 4.4 mol of water) prepared in the same manner as in the first step was introduced into a 5 L PFA vessel. Then, while cooling to -10°C in an ice bath, 3564 g (178.13 mol) of anhydrous HF was added dropwise over 120 minutes. The prepared solution was transferred to a 20 L PFA-lined reactor. The reactor was depressurized to -0.03 MPaG using a decompression pump.
  • This solution was introduced into a 5 m 1 ⁇ 4 inch PFA tube heated to 150°C in an oil bath at 800 mL/min using a diaphragm pump. After heating, gas and liquid were separated, and the liquid component was returned to the reactor. The HF in the gaseous components was liquefied by cooling the condenser to -60°C, and then returned to the reactor in the same manner as the liquid components. The generated phosphorus pentafluoride passed through the condenser and was then collected as lithium hexafluorophosphate in a trap containing about 4 L of LiF/EMC solution containing 250 g (9.65 mol) of LiF (reaction temperature: 25°C).
  • the liquid in the reactor was circulated between the heated PFA tube and the reactor for 3 hours, resulting in 518 g (3.42 mol, yield 28.8%) of lithium hexafluorophosphate.
  • the production rate of lithium hexafluorophosphate at this time was 172.5 g/hour.
  • 10.0 mol (yield 84%) of lithium hexafluorophosphate was obtained after 19 hours of operation.
  • the mixture was separated into gas and liquid, and the liquid component was returned to the reactor.
  • the HF in the gas component was liquefied by cooling the condenser to -60°C, and then returned to the reactor in the same manner as the liquid component.
  • the generated phosphorus pentafluoride passed through a condenser and was then collected as lithium hexafluorophosphate in a trap containing about 5 L of LiF/EMC solution containing 320 g (12.34 mol) of LiF (reaction temperature: 25° C.).
  • the liquid in the reactor was circulated between the heated PFA tube and the reactor for 3 hours, resulting in 130 g (0.86 mol, 7% yield) of lithium hexafluorophosphate.
  • the production rate of lithium hexafluorophosphate at this time was 43.6 g/hour.
  • 9.6 mol (79% yield) of lithium hexafluorophosphate was obtained after 31 hours of operation.
  • the generated phosphorus pentafluoride was collected as lithium hexafluorophosphate in a trap containing about 200mL of LiF/DMC solution containing 5.1g of LiF. As a result, lithium hexafluorophosphate was obtained with a yield of 91%.
  • the amount of phosphorus pentafluoride generated was equivalent to 19.9 g.
  • the amount of sulfuric acid waste was 96.7 g of 95% sulfuric acid, including the amount of fuming sulfuric acid used, phosphoric acid, and water derived from the reaction. This means that 4.0 g of sulfuric acid becomes waste per 1 g of phosphorus pentafluoride produced.
  • the generated phosphorus pentafluoride was collected as lithium hexafluorophosphate in a trap containing about 200 mL of LiF/DMC solution containing 4.5 g (0.17 mol) of LiF. As a result, lithium hexafluorophosphate was obtained with a yield of 97%.
  • the amount of phosphorus pentafluoride generated is equivalent to 21.2 g.
  • the amount of sulfuric acid waste is 103.9 g of 100% sulfuric acid, which includes phosphoric acid and sulfuric acid generated from fluorosulfonic acid hydrolyzed by water from the reaction. This means that 4.9 g of sulfuric acid is generated as waste per 1 g of phosphorus pentafluoride produced.
  • the method for producing phosphorus pentafluoride of the present invention is not only economical and enables the recycling of hydrogen fluoride and sulfuric acid by using sulfuric acid to dehydrate hexafluorophosphate hydrate, but also a sustainable, clean method that reduces emissions of substances that have an environmental impact by producing almost no sulfuric acid waste.
  • the present invention not only reduces hydrogen chloride waste, but also effectively reduces sulfuric acid waste compared to conventional techniques, making it possible to produce phosphorus pentafluoride in a clean manner.
  • the method of the present invention is also economical in that it uses inexpensive materials that are relatively easy to handle.
  • the phosphorus pentafluoride obtained by this method can be used to produce hexafluorophosphate in an industrially advantageous manner.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Ce procédé de production de pentafluorure de phosphore comprend une étape de déshydratation pour déshydrater l'hydrate d'hexafluorophosphate à l'aide d'acide sulfurique ayant une teneur en trioxyde de soufre inférieure à 5 % en masse.　Il est également préférable d'inclure les étapes suivantes a) et b). a) Une étape de concentration de l'acide sulfurique après l'étape de déshydratation. b) Une étape dans laquelle l'acide sulfurique est réutilisé dans la production de pentafluorure de phosphore à l'aide de l'acide sulfurique concentré à l'étape a) dans la déshydratation de l'hydrate d'hexafluorophosphate.　Il est également préférable que l'étape de déshydratation soit effectuée en présence de fluorure d'hydrogène, et que l'étape c) soit incluse avant l'étape a). c) Une étape de récupération du fluorure d'hydrogène après l'étape de déshydratation.
PCT/JP2024/046305 2023-12-28 2024-12-27 Procédé de production de pentafluorure de phosphore et procédé de production d'hexafluorophosphate Pending WO2025143183A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023222059 2023-12-28
JP2023-222059 2023-12-28

Publications (1)

Publication Number Publication Date
WO2025143183A1 true WO2025143183A1 (fr) 2025-07-03

Family

ID=96218080

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/046305 Pending WO2025143183A1 (fr) 2023-12-28 2024-12-27 Procédé de production de pentafluorure de phosphore et procédé de production d'hexafluorophosphate

Country Status (1)

Country Link
WO (1) WO2025143183A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10245211A (ja) * 1996-12-03 1998-09-14 Elf Atochem Sa 三塩化リンのフッ素化による五フッ化リンの合成
JP2014001136A (ja) * 2013-08-21 2014-01-09 Stella Chemifa Corp 五フッ化リン及び六フッ化リン酸塩の製造方法
WO2014156995A1 (fr) * 2013-03-25 2014-10-02 三井化学株式会社 Procédé de fabrication de pentafluorure de phosphore, procédé de fabrication d'hexafluorophosphate de lithium, hexafluorophosphate de lithium, électrolyte non aqueux pour des cellules et accumulateur au lithium
WO2023131011A1 (fr) * 2022-01-06 2023-07-13 深圳市研一新材料有限责任公司 Hexafluorophosphate, pentafluorure de phosphore, leur procédé de préparation et leur application
CN117361458A (zh) * 2023-09-27 2024-01-09 福华通达化学股份公司 一种五氟化磷的连续生产方法
CN117819498A (zh) * 2024-01-15 2024-04-05 新乡意盛科技有限公司 一种五氟化磷的制备方法
CN221071039U (zh) * 2023-09-27 2024-06-04 福华通达化学股份公司 一种五氟化磷的连续生产系统

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10245211A (ja) * 1996-12-03 1998-09-14 Elf Atochem Sa 三塩化リンのフッ素化による五フッ化リンの合成
WO2014156995A1 (fr) * 2013-03-25 2014-10-02 三井化学株式会社 Procédé de fabrication de pentafluorure de phosphore, procédé de fabrication d'hexafluorophosphate de lithium, hexafluorophosphate de lithium, électrolyte non aqueux pour des cellules et accumulateur au lithium
JP2014001136A (ja) * 2013-08-21 2014-01-09 Stella Chemifa Corp 五フッ化リン及び六フッ化リン酸塩の製造方法
WO2023131011A1 (fr) * 2022-01-06 2023-07-13 深圳市研一新材料有限责任公司 Hexafluorophosphate, pentafluorure de phosphore, leur procédé de préparation et leur application
CN117361458A (zh) * 2023-09-27 2024-01-09 福华通达化学股份公司 一种五氟化磷的连续生产方法
CN221071039U (zh) * 2023-09-27 2024-06-04 福华通达化学股份公司 一种五氟化磷的连续生产系统
CN117819498A (zh) * 2024-01-15 2024-04-05 新乡意盛科技有限公司 一种五氟化磷的制备方法

Similar Documents

Publication Publication Date Title
EP3024779B1 (fr) Synthèse de bis(fluorosulfonyl)imide d'hydrogène
KR101559591B1 (ko) 5불화인 및 6불화인산염의 제조방법
KR102160319B1 (ko) 비스(플루오로설폰일)이미드의 합성
TWI471261B (zh) Phosphorus pentafluoride and hexafluorophosphate
JP5146149B2 (ja) トリフルオロメタンスルホニルフルオリドの精製方法
MXPA03006112A (es) Preparacion de pentafluoruro de fosforo.
JP5341425B2 (ja) フッ化物ガスの製造方法
KR101521069B1 (ko) 디플루오로인산염의 정제 방법
KR101488146B1 (ko) 디플루오로인산염의 제조 방법
KR20160065820A (ko) 오불화인의 정제 방법
JP5169880B2 (ja) トリフルオロメタンスルホニルフルオリドの精製方法
JP2017137221A (ja) フッ化水素酸と硝酸の回収方法
KR20120057623A (ko) 비스술포닐이미드암모늄염, 비스술포닐이미드 및 비스술포닐이미드리튬염의 제조 방법
WO2025143183A1 (fr) Procédé de production de pentafluorure de phosphore et procédé de production d'hexafluorophosphate
JP2010059071A (ja) トリフルオロメタンスルホニルフルオリドの精製方法
US10941089B2 (en) Processes for producing trifluoroiodomethane using trifluoroacetic acid
KR20040054623A (ko) 5불화인 제조방법
EP4242173A1 (fr) Purification d'hydrogène bis(fluorosulfonyl)imide
JP6330064B1 (ja) ヨウ化水素酸の製造方法及びヨウ化金属水溶液の製造方法
CN119591131A (zh) 一种氟代磷酸盐的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24913069

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2025567310

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025567310

Country of ref document: JP