KR20060105036A - Concentration of Phosphorus Pentafluoride in a Mixture of Phosphorus Pentafluoride and Hydrogen Chloride - Google Patents
Concentration of Phosphorus Pentafluoride in a Mixture of Phosphorus Pentafluoride and Hydrogen Chloride Download PDFInfo
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- KR20060105036A KR20060105036A KR1020067012869A KR20067012869A KR20060105036A KR 20060105036 A KR20060105036 A KR 20060105036A KR 1020067012869 A KR1020067012869 A KR 1020067012869A KR 20067012869 A KR20067012869 A KR 20067012869A KR 20060105036 A KR20060105036 A KR 20060105036A
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- hydrogen chloride
- phosphorus
- mixture
- phosphorus pentafluoride
- fluoride
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 title description 7
- VVRKSAMWBNJDTH-UHFFFAOYSA-N difluorophosphane Chemical compound FPF VVRKSAMWBNJDTH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 3
- QHLAYFMDLBCWIU-UHFFFAOYSA-N FP(F)F.Cl Chemical compound FP(F)F.Cl QHLAYFMDLBCWIU-UHFFFAOYSA-N 0.000 claims 1
- 238000004508 fractional distillation Methods 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QRMKENJMCGAGNO-UHFFFAOYSA-N Cl.P(F)(F)(F)(F)F Chemical compound Cl.P(F)(F)(F)(F)F QRMKENJMCGAGNO-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
본 발명에 따르면, 오불화인과 염화수소의 혼합물은 30 내지 60bar에서 가압 증류에 의해 분리되거나 농축되며, 이때 분별 증류는 오불화인의 임계 온도보다 약간 낮거나 그 이상이지만 염화수소의 임계 온도보다 낮은 온도 범위에서 일어난다. According to the invention, the mixture of phosphorus fluoride and hydrogen chloride is separated or concentrated by pressure distillation at 30 to 60 bar, wherein the fractional distillation is in the temperature range slightly below or above the critical temperature of phosphorus fluoride but below the critical temperature of hydrogen chloride. Happens.
Description
본 발명은 오불화인(PF5)과 염화수소(HCl)의 혼합물 중 오불화인의 분리 방법 또는 오불화인과 염화수소의 혼합물 중 오불화인의 농축 방법에 관한 것이다. The present invention relates to a method for separating phosphorus fluoride in a mixture of phosphorus fluoride (PF 5 ) and hydrogen chloride (HCl) or a method for concentrating phosphorus fluoride in a mixture of phosphorus fluoride and hydrogen chloride.
오불화인은, 예를 들면 삼염화인을 불화수소 및 염소를 사용하여 변환시켜 제조한다(유럽특허 제0 816 287호). Phosphorus pentafluoride is produced by, for example, converting phosphorus trichloride using hydrogen fluoride and chlorine (European Patent No. 0 816 287).
PCl3 + 5HF + Cl2 → PF5 + 5HCl PCl 3 + 5HF + Cl 2 → PF 5 + 5HCl
상기 반응은 통상적으로 염소의 존재하에 수행되어, 3가의 출발 화합물을 5가의 단계로 산화시킨다. 상기 방법은 유리하게 연속적으로 수행되며, 또한 배치 방식으로도 수행될 수 있다. The reaction is usually carried out in the presence of chlorine to oxidize the trivalent starting compound in a pentavalent step. The method is advantageously carried out continuously and can also be carried out in a batch manner.
연속적인 방식의 방법에서 반응기에는 3가의 출발 화합물이 과량으로 존재한다. 또한 산화제가 과량으로 사용될 수 있다. 또한, 반응물은 화학양론적 양으로 사용될 수 있다. In a continuous manner the reactor is in excess in the trivalent starting compound. Oxidizers can also be used in excess. In addition, the reactants may be used in stoichiometric amounts.
불화수소산은 바람직하게 화학양론적 필요량으로 사용된다. 불화수소산이 과량으로 사용되는 경우에는 이들이 동시에 용매로서 기능할 수 있다. 예를 들면, HF는 반응 혼합물의 70중량% 또는 그 이상으로 사용될 수 있다. 산화제를 가함으로써 반응 속도를 조절할 수 있다. Hydrofluoric acid is preferably used in stoichiometric requirements. When hydrofluoric acid is used in excess, they can simultaneously function as a solvent. For example, HF can be used at 70% by weight or more of the reaction mixture. The reaction rate can be controlled by adding an oxidizing agent.
일반적으로 오불화인은 다섯 배 양의 염화수소와의 혼합물로 수득된다. 이러한 혼합물로부터 오불화인은, 불화수소를 육불화인산으로 변환시키고 이어서 이 화합물을 열분해시켜 목적하는 오불화인을 수득함으로써 분리되는 것으로 종종 언급된다. 그러나 상기 정제 방법은 상당한 비용의 추가 장치를 필요로 하기 때문에 거의 사용되지 않는다. Phosphorus fluoride is generally obtained in a mixture with five times the amount of hydrogen chloride. Phosphorus pentafluoride from such mixtures is often referred to as being separated by converting hydrogen fluoride to phosphoric phosphate and then pyrolyzing this compound to give the desired phosphorus pentafluoride. However, the purification method is rarely used because it requires a considerable additional cost device.
본 발명의 목적은 오불화인과 염화수소의 혼합물의 분리 방법 또는 오불화인과 염화수소의 혼합물 중 오불화인의 농축 방법을 제공하는 것이다. It is an object of the present invention to provide a method for separating a mixture of phosphorus fluoride and hydrogen chloride or a method for concentrating phosphorus fluoride in a mixture of phosphorus fluoride and hydrogen chloride.
본 발명에 따르면, 30 내지 60bar의 압력 범위 및 오불화인의 임계 온도 보다 약간 낮거나 그 이상의 온도 범위에서 가압 증류에 의해 염화수소의 함량은 최소화될 수 있다. 이에 의해 염화수소가 희박해진 오불화인-염화수소 혼합물이 수득된다. According to the invention, the content of hydrogen chloride can be minimized by pressure distillation in the pressure range of 30 to 60 bar and in the temperature range slightly below or above the critical temperature of phosphorus fluoride. This gives a phosphorus pentafluoride-hydrogen chloride mixture in which the hydrogen chloride is lean.
통상의 압력에서는 PF5/HCl-혼합물을 분별증류시키기 어려운데, 두 화합물의 끓는점이 사실상 동일하기 때문이다. At ordinary pressures, it is difficult to fractionate the PF 5 / HCl-mixture because the boiling points of the two compounds are substantially the same.
본 발명에 따르면, 가압 증류는 30 내지 60 bar의 압력 범위, 및 오불화인의 임계 온도보다 약간 낮거나 높지만, 염화수소의 임계 온도보다 낮은 온도 범위에서 수행된다. 가압 증류는 -10 내지 51.4℃의 온도에서 수행된다. According to the invention, the pressure distillation is carried out in a pressure range of 30 to 60 bar and in a temperature range slightly below or above the critical temperature of phosphorus fluoride, but below the critical temperature of hydrogen chloride. Pressurized distillation is carried out at a temperature of -10 to 51.4 ° C.
실시예에서 가압 증류는 오불화인의 임계 온도보다 약간 낮은 -10 내지 20℃에서 수행된다. Pressurized distillation in the examples is carried out at -10 to 20 ° C slightly below the critical temperature of phosphorus fluoride.
또 다른 실시예에서 가압 증류는 염화수소의 임계 온도 미만인 20 내지 51.4℃에서 수행된다. In another embodiment, the pressure distillation is carried out at 20-51.4 ° C., below the critical temperature of hydrogen chloride.
분리는 염화수소의 임계 온도 미만에서 이루어지기 때문에, 염화수소는 증류 컬럼의 바닥부에 액체 형태로 분리될 수 있다. Since the separation takes place below the critical temperature of the hydrogen chloride, the hydrogen chloride can be separated in liquid form at the bottom of the distillation column.
기체상 오불화인은 증류 컬럼의 상부에서 분리된다. Gas phase phosphorus fluoride is separated at the top of the distillation column.
분리 인수 α는 다음의 등식으로 결정된다.The separation factor α is determined by the following equation.
본 발명에 따른 조건하에 바람직한 실시예에서 오불화인의 임계점을 초과하여 가압 증류 처리되며, 이때 추가로 압력을 상승시켜도 더 이상 액화되지는 않는다. 따라서, 오불화인은 상승된 압력에서도 기체상으로 존재한다. 염화수소는 언급된 조건하에 액체상으로 농축되며, 이로써 상들에서의 몰비가 변화한다. Under preferred conditions under the conditions of the invention, pressure distillation is carried out above the critical point of phosphorus fluoride, at which point further pressure is no longer liquefied. Thus, phosphorus fluoride is present in the gas phase even at elevated pressures. Hydrogen chloride is concentrated into the liquid phase under the conditions mentioned, thereby changing the molar ratio in the phases.
이후의 실시예는 본 발명을 상세히 설명하지만 이에 한정되는 것은 아니다.The following examples illustrate the present invention in detail but are not limited thereto.
가압 증류 설비에 PF5/HCl-혼합물을 언급된 조건하에 분별증류한다. The PF 5 / HCl-mixture is fractionally distilled under the conditions mentioned in the pressurized distillation plant.
본 발명에 따라 정제된 오불화인은 바람직하게 육불화인산리튬을 제조하기 위한 출발물질로서 사용되고 매우 순수한 육불화인산리튬을 제조할 수 있다. The phosphorus pentafluoride purified according to the invention is preferably used as a starting material for producing lithium hexafluorophosphate and can produce very pure lithium hexafluorophosphate.
상기 화합물을 제조하기 위해 오불화인을 리튬 할로겐화물 및 액체 불화수소로 이루어진 용액 또는 현탁액에 가한다. 이때, 오불화인은 다음의 화학 반응식과 같이 불화리튬과 반응하여 육불화인산리튬을 형성한다. Phosphorus fluoride is added to a solution or suspension of lithium halide and liquid hydrogen fluoride to prepare the compound. At this time, the phosphorus fluoride reacts with lithium fluoride to form lithium hexafluorophosphate as in the following chemical reaction formula.
LiF + PF5 → LiPF6 LiF + PF 5 → LiPF 6
육불화인산리튬은 재충전이 가능한 리튬 배터리용 전도 염으로서 특히 필요하다. 이러한 이용 영역에 대해서는, 순도가 높은 제품을 사용할 수 있는 경우에 유리하다. Lithium hexafluorophosphate is particularly needed as a conducting salt for rechargeable lithium batteries. This use area is advantageous when a product with high purity can be used.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10355696.6 | 2003-11-28 | ||
| 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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20060105036A true KR20060105036A (en) | 2006-10-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020067012869A Withdrawn KR20060105036A (en) | 2003-11-28 | 2004-11-18 | Concentration of Phosphorus Pentafluoride in a Mixture of Phosphorus Pentafluoride and Hydrogen Chloride |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2007513853A (en) |
| KR (1) | KR20060105036A (en) |
| CN (1) | CN1886337A (en) |
| DE (1) | DE10355696A1 (en) |
| WO (1) | WO2005061381A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200808656A (en) * | 2006-04-27 | 2008-02-16 | Solvay Fluor Gmbh | Reversible water-free process for the separation of acid-containing gas mixtures |
| US8784763B2 (en) * | 2009-03-13 | 2014-07-22 | Honeywell International Inc. | Methods and reactor designs for producing phosphorus pentafluoride |
| JP5803098B2 (en) * | 2010-12-17 | 2015-11-04 | ダイキン工業株式会社 | Method for producing phosphorus pentafluoride |
| CN109052349A (en) * | 2018-11-07 | 2018-12-21 | 四川大学 | The continuous preparation method of phosphorus pentafluoride |
| 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 |
| CN116514143A (en) * | 2023-05-23 | 2023-08-01 | 江苏新泰材料科技有限公司 | A kind of liquid lithium hexafluorophosphate and its preparation process |
| CN116730289A (en) * | 2023-07-12 | 2023-09-12 | 天津大学浙江研究院(绍兴) | Method for preparing electronic grade hydrogen chloride and hydrogen fluoride from fluorine-containing lithium salt synthesis tail gas |
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| JP2987713B2 (en) * | 1990-11-09 | 1999-12-06 | 株式会社トーケムプロダクツ | Method for producing high-purity hexafluorophosphoric acid compound |
| US6645451B1 (en) * | 1996-06-26 | 2003-11-11 | Solvay Fluor Und Derivate Gmbh | Method of preparing inorganic pentafluorides |
| FR2781474B1 (en) * | 1998-07-07 | 2000-09-08 | Atochem Elf Sa | INDUSTRIAL PROCESS FOR THE CONTINUOUS MANUFACTURE OF A PF5 MIXTURE AND OF HC1 AND MIXTURE THUS OBTAINED |
-
2003
- 2003-11-28 DE DE10355696A patent/DE10355696A1/en not_active Withdrawn
-
2004
- 2004-11-18 CN CNA2004800351248A patent/CN1886337A/en active Pending
- 2004-11-18 JP JP2006540326A patent/JP2007513853A/en active Pending
- 2004-11-18 KR KR1020067012869A patent/KR20060105036A/en not_active Withdrawn
- 2004-11-18 WO PCT/EP2004/013098 patent/WO2005061381A1/en not_active Ceased
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| Publication number | Publication date |
|---|---|
| JP2007513853A (en) | 2007-05-31 |
| WO2005061381A1 (en) | 2005-07-07 |
| CN1886337A (en) | 2006-12-27 |
| DE10355696A1 (en) | 2005-06-23 |
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| PA0105 | International application |
Patent event date: 20060627 Patent event code: PA01051R01D Comment text: International Patent Application |
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| PG1501 | Laying open of application | ||
| PC1203 | Withdrawal of no request for examination | ||
| WITN | Application deemed withdrawn, e.g. because no request for examination was filed or no examination fee was paid |