JP2007513853A - Method for increasing the content of phosphorus pentafluoride in a phosphorus pentafluoride-hydrogen chloride mixture - Google Patents

Method for increasing the content of phosphorus pentafluoride in a phosphorus pentafluoride-hydrogen chloride mixture Download PDF

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JP2007513853A
JP2007513853A JP2006540326A JP2006540326A JP2007513853A JP 2007513853 A JP2007513853 A JP 2007513853A JP 2006540326 A JP2006540326 A JP 2006540326A JP 2006540326 A JP2006540326 A JP 2006540326A JP 2007513853 A JP2007513853 A JP 2007513853A
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phosphorus pentafluoride
hydrogen chloride
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chloride mixture
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ベーゼ オラフ
パルスヘルム シュテファン
グロースマン アンドレアス
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/10—Halides or oxyhalides of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
    • 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

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Abstract

五弗化燐−塩化水素−混合物の分離または含量の増加は、３０〜６０バールでの圧力蒸留によって行なわれ、この場合分別は、五弗化燐の臨界温度をまさに下廻る温度範囲または五弗化燐の臨界温度をまさに上廻る温度範囲で、しかも塩化水素の臨界温度を下廻って実施される。  Separation or increase in content of the phosphorus pentafluoride-hydrogen chloride mixture is effected by pressure distillation at 30-60 bar, in which fractionation is carried out in a temperature range just below the critical temperature of phosphorus pentafluoride or in pentafluoride. It is carried out in a temperature range just above the critical temperature of phosphorus phosphide and below the critical temperature of hydrogen chloride.

Description

本発明は、五弗化燐（ＰＦ５）−塩化水素（ＨＣｌ）−混合物を分離する方法または五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法に関する。 The present invention relates to a method for separating phosphorus pentafluoride (PF 5 ) -hydrogen chloride (HCl) -mixture or a method for increasing the content of phosphorus pentafluoride in a phosphorus pentafluoride-hydrogen chloride mixture.

五弗化燐は、例えば三塩化燐を弗化水素および塩素と反応させることによって製造される（欧州特許第０８１６２８７号明細書）。   Phosphorus pentafluoride is produced, for example, by reacting phosphorus trichloride with hydrogen fluoride and chlorine (EP 0816287).

ＰＣｌ３ ＋ ５ ＨＦ ＋ Ｃｌ２ → ＰＦ５ ＋ ５ ＨＣｌ
この反応は、通常、塩素の存在で実施され、三価の出発化合物を五価の段階に酸化する。この場合、この方法を連続的に実施することは、有利であることが証明され、この場合には、バッチ式の実施も、同様に可能である。 PCl 3 + 5 HF + Cl 2 → PF5 + 5 HCl
This reaction is usually carried out in the presence of chlorine and oxidizes the trivalent starting compound to the pentavalent stage. In this case, it is proved advantageous to carry out the process continuously, in which case a batch-type implementation is likewise possible.

連続的な方法の場合、反応器中には、三価の出発化合物が存在する。同様に、酸化剤を過剰量で使用することも可能である。反応体の化学量論的量の使用も同様に可能である。   In the case of a continuous process, trivalent starting compounds are present in the reactor. Similarly, it is possible to use an excess of oxidizing agent. The use of stoichiometric amounts of reactants is possible as well.

フッ酸は、有利に化学量論的な必要量で使用される。このフッ酸を過剰量で使用する場合には、フッ酸は、同時に溶剤として使用することができる。例えば、ＨＦは、反応混合物に対して７０質量％またはそれ以上であることができる。反応速度は、酸化剤の計量供給によって制御されることができる。   Hydrofluoric acid is preferably used in a stoichiometric amount. When this hydrofluoric acid is used in an excess amount, the hydrofluoric acid can be used as a solvent at the same time. For example, HF can be 70% by weight or more based on the reaction mixture. The reaction rate can be controlled by metering the oxidant.

五弗化燐は、一般に５倍量の塩化水素との混合物で得ることができる。前記混合物からの五弗化燐の単離、例えば、弗化水素との反応によってヘキサフルオロ燐酸に変え、引続きこの化合物を熱分解することによって望ましい五弗化燐に変えることは、時折、記載されている。しかし、この精製は、多大に付加的な装置的費用を必要とし、したがってめったに利用されない。   Phosphorus pentafluoride can generally be obtained in a mixture with 5 times the amount of hydrogen chloride. Isolation of phosphorus pentafluoride from the mixture, for example, conversion to hexafluorophosphoric acid by reaction with hydrogen fluoride and subsequent conversion to the desired phosphorus pentafluoride by thermal decomposition of this compound, is sometimes described. ing. However, this purification requires much additional equipment costs and is therefore rarely utilized.

本発明の課題は、五弗化燐−塩化水素−混合物を分離する方法を提供するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法を提供することである。   The object of the present invention is to provide a method for separating a phosphorus pentafluoride-hydrogen chloride mixture or to increase the content of phosphorus pentafluoride in a phosphorus pentafluoride-hydrogen chloride mixture. is there.

３０〜６０バールの圧力範囲および五弗化燐の臨界温度をまさに下廻る温度ならびに五弗化燐をまさに上廻る温度で圧力蒸留することによって、塩化水素含量を最少化することができることが見出された。それによって、塩化水素の含量が減少された五弗化燐−塩化水素−混合物を得ることができる。   It has been found that the hydrogen chloride content can be minimized by pressure distillation at a pressure range of 30-60 bar and a temperature just below the critical temperature of phosphorus pentafluoride and just above phosphorus pentafluoride. It was done. Thereby, a phosphorus pentafluoride-hydrogen chloride mixture with a reduced hydrogen chloride content can be obtained.

ＰＦ５／ＨＣｌ混合物の常圧下での分別は、困難である。それというのも、双方の化合物の沸騰温度は、実際に等しいからである。 Fractionation of PF 5 / HCl mixtures under normal pressure is difficult. This is because the boiling temperatures of both compounds are actually equal.

Figure 2007513853
Figure 2007513853

本発明によれば、圧力蒸留は、３０〜６０バールの圧力範囲および五弗化燐の臨界温度をまさに下廻る温度、有利には五弗化燐の臨界温度をまさに上廻る温度で、しかも塩化水素の臨界温度を下廻って実施される。圧力蒸留は、−１０℃〜５１．４℃の温度で実施される。   According to the invention, the pressure distillation is carried out at a pressure range of 30-60 bar and at a temperature just below the critical temperature of phosphorus pentafluoride, preferably just above the critical temperature of phosphorus pentafluoride, and chloride. Performed below the critical temperature of hydrogen. Pressure distillation is carried out at a temperature of -10 ° C to 51.4 ° C.

１つの実施態様において、圧力蒸留は、五弗化燐の臨界温度をまさに下廻る温度で−１０℃〜２０℃で実施される。   In one embodiment, the pressure distillation is carried out at -10 ° C to 20 ° C at a temperature just below the critical temperature of phosphorus pentafluoride.

別の実施態様において、圧力蒸留は、塩化水素の臨界温度を下廻る温度で２０〜５１．４℃で実施される。   In another embodiment, the pressure distillation is carried out at 20-51.4 ° C. at a temperature below the critical temperature of hydrogen chloride.

分離は、塩化水素の臨界点を下廻って行なわれるので、塩化水素は、液状の形で蒸留塔の塔底部から導出されうる。   Since the separation takes place below the critical point of hydrogen chloride, the hydrogen chloride can be derived from the bottom of the distillation column in liquid form.

ガス状の五弗化燐は、蒸留塔の塔頂部から取り出される。   Gaseous phosphorus pentafluoride is removed from the top of the distillation column.

分離ファクターは、次の等式によって定められる。   The separation factor is defined by the following equation:

Figure 2007513853
Figure 2007513853

本発明による条件下で好ましい実施態様においては、五弗化燐の臨界点を上廻って作業され、即ちさらに圧力を上昇させた場合でももはや液化することはできない。従って、五弗化燐は、圧力を上昇させた場合でも気相でのみ存在する。塩化水素は、記載された条件下で液相で含量が増加され、それによってこの相中でのモル比は、変化する。   In the preferred embodiment under the conditions according to the invention, the critical point of phosphorus pentafluoride is exceeded, i.e. it can no longer liquefy even if the pressure is increased further. Thus, phosphorus pentafluoride is present only in the gas phase even when the pressure is increased. Hydrogen chloride is increased in content in the liquid phase under the conditions described, whereby the molar ratio in this phase changes.

次の実施例により、本発明を詳説するが、しかし、本発明は、制限されるものではない。   The following examples illustrate the invention but are not intended to limit the invention.

実施例：
圧力蒸留装置中でＰＦ５／ＨＣｌ混合物を記載された条件下で分別した。 Example:
The PF 5 / HCl mixture was fractionated in the pressure distillation apparatus under the conditions described.

Figure 2007513853
Figure 2007513853

本発明により精製された五弗化燐を特にリチウムヘキサフルオロホスフェートの製造のための出発物質として使用し、極めて純粋なリチウムヘキサフルオロホスフェートの製造を可能にする。   Phosphorus pentafluoride purified according to the invention is used as a starting material, in particular for the production of lithium hexafluorophosphate, allowing the production of very pure lithium hexafluorophosphate.

前記化合物の製造のために、五弗化燐をハロゲン化リチウムおよび液状弗化水素からなる溶液または懸濁液中に導入する。この場合、五弗化燐は、フッ化リチウムと次の方程式：
ＬｉＦ ＋ ＰＦ５ → ＬｉＰＦ６
により反応し、リチウムヘキサフルオロホスフェートに変わる。 For the preparation of the compound, phosphorus pentafluoride is introduced into a solution or suspension consisting of lithium halide and liquid hydrogen fluoride. In this case, phosphorus pentafluoride is lithium fluoride and the following equation:
LiF + PF 5 → LiPF 6
To give lithium hexafluorophosphate.

リチウムヘキサフルオロホスフェートは、なかんずく再充電可能なリチウム電池のための導電性塩として必要とされている。前記の使用範囲にとって、高い純度の生成物を使用することができることは、利点である。   Lithium hexafluorophosphate is needed, among other things, as a conductive salt for rechargeable lithium batteries. For the above range of use, it is an advantage that highly pure products can be used.

Claims (5)

五弗化燐−塩化水素−混合物を分離するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法において、３０〜６０バールで塩化水素の臨界温度を下廻る温度で圧力蒸留を実施することを特徴とする、五弗化燐−塩化水素−混合物を分離するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法。   In the process of separating the phosphorus pentafluoride-hydrogen chloride mixture or increasing the content of phosphorus pentafluoride in the phosphorus pentafluoride-hydrogen chloride mixture, below the critical temperature of hydrogen chloride at 30-60 bar. A process for separating a phosphorus pentafluoride-hydrogen chloride mixture or increasing the content of phosphorus pentafluoride in a phosphorus pentafluoride-hydrogen chloride mixture, characterized in that pressure distillation is carried out at temperature. 圧力蒸留を塩化水素の臨界温度を下廻る温度および五弗化燐の臨界温度を上廻る温度で実施する、請求項１記載の五弗化燐−塩化水素−混合物を分離するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法。   2. The phosphorus pentafluoride-hydrogen chloride mixture according to claim 1, wherein the pressure distillation is carried out at a temperature below the critical temperature of hydrogen chloride and above the critical temperature of phosphorus pentafluoride. A method for increasing the content of phosphorus pentafluoride in a phosphorus-hydrogen chloride mixture. 圧力蒸留を２０〜５１．４℃の温度で実施する、請求項１または２記載の五弗化燐−塩化水素−混合物を分離するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法。   The pressure distillation is carried out at a temperature of from 20 to 51.4 ° C. The phosphorus pentafluoride-hydrogen chloride mixture according to claim 1 or 2 is separated or pentafluorination in the phosphorus pentafluoride-hydrogen chloride mixture. A method for increasing the phosphorus content. 圧力蒸留を五弗化燐の臨界温度をまさに下廻る温度で実施する、請求項１記載の五弗化燐−塩化水素−混合物を分離するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法。   2. The pressure-distillation is carried out at a temperature just below the critical temperature of phosphorus pentafluoride, or the phosphorus pentafluoride-hydrogen chloride mixture according to claim 1 is separated or five in the phosphorus pentafluoride-hydrogen chloride mixture. A method for increasing the content of phosphorus fluoride. 圧力蒸留を−１０〜２０℃の温度で実施する、請求項４記載の五弗化燐−塩化水素−混合物を分離するかまたは五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法。   5. The phosphorus pentafluoride-hydrogen chloride mixture according to claim 4, wherein the pressure distillation is carried out at a temperature of −10 to 20 ° C., or the content of phosphorus pentafluoride in the phosphorus pentafluoride-hydrogen chloride mixture. How to increase.
JP2006540326A 2003-11-28 2004-11-18 Method for increasing the content of phosphorus pentafluoride in a phosphorus pentafluoride-hydrogen chloride mixture Pending JP2007513853A (en)

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DE10355696A DE10355696A1 (en) 2003-11-28 2003-11-28 Separation of phosphorus pentafluoride from a mixture with hydrogen chloride involves pressure distillation at above or just below the phosphorus pentafluoride critical temperature
PCT/EP2004/013098 WO2005061381A1 (en) 2003-11-28 2004-11-18 Method for enriching phosphorus pentafluoride in a mixture of phosphorus pentafluoride and hydrogen chloride

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WO2010105120A3 (en) * 2009-03-13 2011-01-13 Honeywell International Inc. Methods and reactor designs for producing phosphorus pentafluoride
JP2012126621A (en) * 2010-12-17 2012-07-05 Daikin Industries Ltd Method for producing phosphorus pentafluoride
CN109052349A (en) * 2018-11-07 2018-12-21 四川大学 The continuous preparation method of phosphorus pentafluoride

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TW200808656A (en) 2006-04-27 2008-02-16 Solvay Fluor Gmbh Reversible water-free process for the separation of acid-containing gas mixtures
CN111410182A (en) * 2020-03-31 2020-07-14 福建省龙德新能源股份有限公司 Method for recycling phosphorus pentafluoride in lithium hexafluorophosphate synthesis tail gas
CN112079367A (en) * 2020-08-11 2020-12-15 江苏新泰材料科技有限公司 Efficient synthesis process of lithium hexafluorophosphate
GB202110642D0 (en) * 2021-07-23 2021-09-08 Mexichem Fluor Sa De Cv Separation method
CN114477114B (en) * 2022-01-25 2024-01-26 上海协柯环保设备有限公司 Equipment and method for rectifying, separating and purifying mixed gas of hydrogen fluoride, phosphorus pentafluoride and hydrogen chloride
CN115072681B (en) * 2022-08-01 2023-07-14 森松（江苏）重工有限公司 Phosphorus pentafluoride gas generator and phosphorus pentafluoride gas generation method

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JPH1053406A (en) * 1996-06-26 1998-02-24 Solvay Fluor & Derivate Gmbh Production of phosphorus pentafluoride and arsenic pentafluoride
JP2002519294A (en) * 1998-07-07 2002-07-02 アトフィナ Industrial continuous production method of a mixture of PF5 and HCl, and a mixture obtained by this method

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JPH04175216A (en) * 1990-11-09 1992-06-23 Tohkem Prod:Kk Production of high-purity hexafluorophosphoric acid compound
JPH1053406A (en) * 1996-06-26 1998-02-24 Solvay Fluor & Derivate Gmbh Production of phosphorus pentafluoride and arsenic pentafluoride
JP2002519294A (en) * 1998-07-07 2002-07-02 アトフィナ Industrial continuous production method of a mixture of PF5 and HCl, and a mixture obtained by this method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010105120A3 (en) * 2009-03-13 2011-01-13 Honeywell International Inc. Methods and reactor designs for producing phosphorus pentafluoride
JP2012520235A (en) * 2009-03-13 2012-09-06 ハネウェル・インターナショナル・インコーポレーテッド Method and reactor design for producing phosphorus pentafluoride
US8784763B2 (en) 2009-03-13 2014-07-22 Honeywell International Inc. Methods and reactor designs for producing phosphorus pentafluoride
JP2012126621A (en) * 2010-12-17 2012-07-05 Daikin Industries Ltd Method for producing phosphorus pentafluoride
CN109052349A (en) * 2018-11-07 2018-12-21 四川大学 The continuous preparation method of phosphorus pentafluoride

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