WO2000056687A1 - Procede de separation de fluorure d'hydrogene de ses melanges avec du 1,1,1,3,3-pentafluorobutane et procede de fabrication de 1,1,1,3,3-pentafluorobutane - Google Patents
Procede de separation de fluorure d'hydrogene de ses melanges avec du 1,1,1,3,3-pentafluorobutane et procede de fabrication de 1,1,1,3,3-pentafluorobutane Download PDFInfo
- Publication number
- WO2000056687A1 WO2000056687A1 PCT/EP2000/002282 EP0002282W WO0056687A1 WO 2000056687 A1 WO2000056687 A1 WO 2000056687A1 EP 0002282 W EP0002282 W EP 0002282W WO 0056687 A1 WO0056687 A1 WO 0056687A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pentafluorobutane
- extraction
- organic solvent
- separation
- pentachlorobutane
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
Definitions
- the present invention relates to a process for the separation of hydrogen fluoride from its mixtures with 1,1,1,3,3-pentafluorobutane.
- 1,1,1,3,3-pentafluorobutane can be prepared by reaction of a suitable chlorinated precursor with hydrogen fluoride, as described for example in patent application EP-A 1- 0699649 on behalf of SOLVAY.
- the mixture of reaction products contains, in addition to the desired 1,1,1,3,3-pentafluorobutane, hydrogen chloride originating from the elimination of the atom (s) chlorine from the starting chlorinated precursor, hydrogen fluoride and, optionally, inert diluents as well as various intermediates or by-products in small quantities.
- the object of the present invention is to provide an efficient process for the separation of hydrogen fluoride from its mixtures with 1,1, 1,3,3 - pentafluorobutane.
- the invention relates to a process for the separation of hydrogen fluoride from its mixtures with 1,1, 1,3, 3 -pentafluorobutane, according to which the separation is carried out by extraction using at least one solvent organic containing at least one chloro (fluoro) butane of general formula CCl a F 3 . a CH 2 CCl b F 2 . b CH 3 (I) with a an integer from 0 to 3, b an integer from 0 to 2, the sum of a and b being at least equal to 1.
- the organic solvent contains 1,1,1,3,3-pentachlorobutane CC1 3 - CH 2 -CC1 2 -CH 3 , a chlorofluorobutane of formula CC1 2 F-CH 2 -CC1 2 -CH 3 , CC1F 2 -CH 2 -CC1 2 -CH 3 , CF 3 -CH 2 -CC1 2 -CH 3 , CF 3 -CH 2 -CC1F-CH 3 , CC1 2 F-CH 2 -CC1F-CH 3 , CC1F 2 -CH 2 -CC1F-CH 3 and CC1F 2 -CH 2 -CF 2 -CH 3 , CC1 3 -CH 2 -CC1F-CH 3 , CC1 3 -CH 2 -CF 2 - CH 3 , CC1 2 F-CH 2 -CF 2 -CH 3 , or mixture of these compounds.
- the organic solvent contains 1,1,1,3,3-pentachlor
- the organic solvent can also contain other halogenated or non-halogenated compounds.
- a non-halogenated compound which may optionally be present in the organic solvent, mention may be made of hydrocarbons containing from 5 to 10 carbon atoms, in particular n-pentane, n-hexane, n-heptane and n-octane.
- halogen compounds which may possibly be present in the organic solvent are chloroform, trichlorethylene, tetrachlorethylene, tetrachloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane , 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1- or 1,1,2- trifluorotrichlorethane, 1,2,3-trichloropropane, perfluorocarbons, bromobenzene, o-dichlorobenzene, p-chlorotoluene, p-chlorotrifluorobenzene and 1,2-dichloro-4-trifluorobenzene, as well as mixtures of these compounds.
- the organic solvent however preferably consists essentially of one or more chloro (fluoro) butanes of general formula (I), 1,1,3,3,3 - pentachlorobutane constituting the
- chlorofluorobutanes of general formula (I) those which contain at least one chlorofluorobutane containing 3 or 4 fluorine atoms are preferred.
- chlorofluorobutanes of general formula (I) containing 3 or 4 fluorine atoms which can be used in the organic solvent are 1,1-dichloro-1,3,3-trifluorobutane (HCFC-363kfc), 3-chloro-1 , l, l, 3-tetrafluorobutane (HCFC-364mfb) and l-chloro-l, l, 3,3-tetrafluorobutane (HCFC-3641fc). These compounds can be obtained when 1,1,1,3,3 -pentachlorobutane is subjected to a hydrofluorination reaction.
- the organic solvent containing at least one chloro (fluoro) butane of general formula (I) containing 3 or 4 fluorine atoms additionally contains 1,1, 1,3, 3 -pentachlorobutane. It may be advantageous to use mixtures containing 1,1, 1,3, 3 -pentachlorobutane, in order to improve the settling properties during extraction.
- Another variant of the process according to the invention relates to a process in which
- an amount of reaction mixture is drawn off which is subjected to a separation operation to recover at least one organic solvent comprising chlorofluorobutanes of general formula (I)
- the organic solvent is used in the separation process according to the invention.
- the separation operation is, for example, distillation or demixing at low temperature.
- the fractions other than the organic solvent can be recycled to the hydrofluorination reaction of 1,1,1,3,3 -pentachlorobutane or can be subjected to subsequent separation steps to recover 1,1,1,3,3 - pentafluorobutane.
- the extraction is carried out on a mixture comprising HF and HFC-365mfc in proportions close to those in which they form an azeotropic composition.
- the mixture can also comprise variable amounts of a chlorofluorobutane of general formula (I).
- chlorofluorobutane is a chlorofluorobutane of general formula (I) in which the sum of a and b is equal to 1 or 2.
- the initial mixture of hydrogen fluoride and HFC-365mfc deviates from the azeotropic composition, it may be advantageous to carry out a distillation beforehand to separate the azeotrope from the excess compound.
- the azeotropic composition is then subjected to extraction.
- the weight ratio between the organic solvent and the mixture of hydrogen fluoride and 1,1,1,3,3-pentafluorobutane is generally at least 0.1. Preferably, one works with a weight ratio of at least 0.2.
- the weight ratio between the organic solvent and the mixture of hydrogen fluoride and 1,1,1,3,3-pentafluorobutane generally does not exceed 10. Preferably, it does not exceed 5.
- the temperature at which the extraction is carried out is generally at least -25 ° C. Preferably, it is around -10 ° C.
- the temperature does not generally exceed 40 ° C. Preferably, it does not exceed 30 ° C.
- the process according to the invention is carried out at a pressure sufficient to maintain the mixture in the liquid state. It can be carried out under the autogenous pressure of the mixture; in this case the pressure is generally less than 3 bar. Alternatively, it can be carried out at a pressure higher than the autogenous pressure. In this case, the total pressure will generally be less than 10 bar; preferably, the pressure used will be less than 3 bar but greater than 1 bar.
- the contacting of the mixture of hydrogen fluoride and 1,1,1,3,3-pentafluorobutane with the organic extraction solvent is carried out in one or more stages, by means of any conventional device.
- liquid-liquid extraction for example by intimate contact using a static mixer, a reactor stirred, a rotary disk extractor, a centrifuge extractor or a column with perforated plates, operating either against the current or co-current.
- the contacting is carried out in a stirred reactor.
- the extraction can be carried out continuously or discontinuously. Preferably, it is carried out continuously.
- an organic phase enriched in 1,1,1,3,3-pentafluorobutane is separated from a phase enriched in hydrogen fluoride (hereinafter called HF phase). This separation can be carried out simply by decantation, but it is also possible to use any other conventional phase separation device, such as centrifugation or separation by hydrocyclone. Separation by decantation is preferred.
- the organic phase mainly comprises the extraction solvent enriched in 1,1, 1,3, 3 -pentafluorobutane, but may also contain a certain amount of hydrogen fluoride. Its composition most often corresponds to the equilibrium composition, determined by the partition coefficients of the different compounds between the hydrogen fluoride and the extraction solvent.
- 1,1,1,3,3 -pentafluorobutane can easily be separated from the other constituents of the organic phase by a conventional separation technique such as distillation.
- the 1,1,1,3,3-pentafluorobutane can then be treated wet to remove the last traces of acidity and / or adsorbed on activated carbon and / or deacidified on zeolite or alumina.
- the solvent can be partially or totally recycled in the extraction step.
- the extraction solvent consists essentially of chloro (fluoro) butanes of the general formula (I)
- it can, after separation of the extracted 1,1,1,3,3-pentafluorobutane, be sent as it is, partially or completely , directly to a 1,1,1,3,3-pentafluorobutane manufacturing reactor by hydrofluorination of such chloro (fluoro) butanes of the general formula (I), in particular by hydrofluorination of 1, 1, 1, 3.3 -pentachlorobutane.
- the HF phase mainly contains hydrogen fluoride depleted in 1,1, 1,3, 3 -pentafluorobutane, but may also contain a significant amount of extraction solvent.
- the extraction solvent consists essentially of chloro (fluoro) butanes of general formula (I)
- the HF phase can be sent as it is directly to a reactor for manufacturing 1,1,1,3,3-pentafluorobutane by hydrofluorination of such chloro (fluoro) butanes of the general formula (I), in particular by hydrofluorination of 1,1,1,3,3-pentachlorobutane.
- solvents containing a compound which is not a precursor of 1,1,1,3,3-pentafluorobutane such a solution is only possible when this compound is sufficiently inert under the reaction conditions.
- the invention also relates to a process for the manufacture of 1,1,1,3,3-pentafluorobutane by hydrofluorination of chloro (fluoro) butanes of the general formula (I), in which the following is introduced into a manufacturing reactor of 1, 1,1,3,3- pentafluorobutane of chloro (fluoro) butanes of the general formula (I) having served as extraction solvent in the separation process according to the invention.
- the reactor is supplied at least partially with the starting product (s) by used extraction solvent.
- used extraction solvent is introduced into the hydrofluorination reactor in the form of the HF phase obtained in the separation process according to the invention.
- used extraction solvent is introduced into the hydrofluorination reactor in the form of the organic phase obtained in the separation process according to the invention, from which the HFC-365mfc has essentially been separated.
- the used solvent supplying the hydrofluorination reactor comprises 1,1,1,3,3-pentachlorobutane, advantageously in a content of at least 50% by weight.
- the content of 1,1,1,3,3-pentachlorobutane in the used solvent is at least 80% by weight.
- the efficiency of the extraction was evaluated by analysis of samples taken in each of the two liquid phases. These liquid samples were taken via an airlock of approximately 5 cm3 after having pressurized the autoclave under 2 bar of nitrogen.
- 1,1,1,3,3-pentachlorobutane extracts approximately twice as much HFC-365mfc as tetrachlorethylene while retaining a high HFC-365mfc / HF ratio in the organic phase.
- the high density of 1,1,1,3,3-pentachlorobutane ensures good properties as regards the settling of the phases during the extraction step.
- 1,1,1,3,3-pentachlorobutane does not form an azeotrope with HFC-365mfc which can therefore be separated from mixtures with 1,1,1,3,3-pentachlorobutane easily by distillation .
- chlorofluorobutane compounds containing 3 or 4 fluorine atoms (HCFC-363kfc, HCFC-364-mfb, HCFC-364-lfc) pure or in mixtures further increases the extraction efficiency of 1.1 , 1,3,3-pentafluorobutane in the organic phase. Extraction rates of 1.1, 1.3, 3 -pentafluorobutane are obtained ranging from approximately 55% to approximately 71%. The extraction rate indicates the percentage of 1,1,1,3,3 -pentafluorobutane extracted in the organic phase compared to the total amount of 1,1,1,3,3 -pentafluorobutane in the starting composition.
- the organic phase freed from 1,1,1,3,3-pentafluorobutane and the HF phase can be recycled to a reactor for manufacturing 1,1,1,3,3-pentafluorobutane.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00912607A EP1165475B1 (fr) | 1999-03-24 | 2000-03-15 | Procede de separation de fluorure d'hydrogene de ses melanges avec du 1,1,1,3,3-pentafluorobutane et procede de fabrication de 1,1,1,3,3-pentafluorobutane |
AU34296/00A AU3429600A (en) | 1999-03-24 | 2000-03-15 | Method for separating hydrogen fluoride from its mixtures with 1,1,1,3,3-pentafluorobutane and method for making 1,1,1,3,3-pentafluorobutane |
DE60007727T DE60007727T2 (de) | 1999-03-24 | 2000-03-15 | Verfahren zur abtrennung von fluorwasserstoff aus seinen mischungen mit 1,1,1,3,3-pentafluorbutan und verfahren zur herstellung von pentafluorbutan |
JP2000606552A JP2002540089A (ja) | 1999-03-24 | 2000-03-15 | フッ化水素と1,1,1,3,3−ペンタフルオロブタンとの混合物からのフッ化水素の分離方法及び1,1,1,3,3−ペンタフルオロブタンの製造方法 |
US09/937,389 US6399841B1 (en) | 1999-03-24 | 2000-03-15 | Method for separating hydrogen fluoride from its mixtures with 1,1,1,3,3-pentafluorobutane and method for making 1,1,1,3,3-pentafluorobutane |
AT00912607T ATE257814T1 (de) | 1999-03-24 | 2000-03-15 | Verfahren zur abtrennung von fluorwasserstoff aus seinen mischungen mit 1,1,1,3,3-pentafluorbutan und verfahren zur herstellung von pentafluorbutan |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR99/03917 | 1999-03-24 | ||
FR9903917A FR2791975B1 (fr) | 1999-03-24 | 1999-03-24 | Procede de separation de fluorure d'hydrogene des ses melanges avec du 1,1,1,3,3-pentafluorobutane et procede de fabrication de 1,1,1,3,3-pentafluorobutane |
FR99/09220 | 1999-07-15 | ||
FR9909220A FR2787443B3 (fr) | 1998-12-18 | 1999-07-15 | Procede de separation de florure d'hydrogene de ses melanges avec du 1,1,1,3,3-pentafluorobutane et procede de fabrication de 1,1,1,3,-pentafluorobutane |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000056687A1 true WO2000056687A1 (fr) | 2000-09-28 |
Family
ID=26234893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/002282 WO2000056687A1 (fr) | 1999-03-24 | 2000-03-15 | Procede de separation de fluorure d'hydrogene de ses melanges avec du 1,1,1,3,3-pentafluorobutane et procede de fabrication de 1,1,1,3,3-pentafluorobutane |
Country Status (8)
Country | Link |
---|---|
US (1) | US6399841B1 (fr) |
EP (1) | EP1165475B1 (fr) |
JP (1) | JP2002540089A (fr) |
AT (1) | ATE257814T1 (fr) |
AU (1) | AU3429600A (fr) |
DE (1) | DE60007727T2 (fr) |
ES (1) | ES2214257T3 (fr) |
WO (1) | WO2000056687A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6673264B2 (en) * | 2001-06-01 | 2004-01-06 | Honeywell International Inc. | Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane and hydrogen fluoride |
FR2855069A1 (fr) * | 2003-05-22 | 2004-11-26 | Solvay | Procede pour la separation d'au moins un compose organique |
EP2078708A1 (fr) * | 1998-12-18 | 2009-07-15 | SOLVAY (Société Anonyme) | Compositions azéotropiques, leur utilisation et procédés de synthèse d'un hydrofluoroalcane |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5208398A (en) * | 1992-04-16 | 1993-05-04 | Elf Atochem N.A., Inc. | HF extraction of R365 from R141B |
EP0699649A1 (fr) * | 1994-09-05 | 1996-03-06 | SOLVAY (Société Anonyme) | Procédé pour l'hydrofluoration de chloro(fluoro)butane |
EP0905085A1 (fr) * | 1997-09-24 | 1999-03-31 | SOLVAY (Société Anonyme) | Procédé de séparation de fluorure d'hydrogène de ses mélanges avec un hydrofluoroalcane contenant de 3 à 6 atomes de carbone |
-
2000
- 2000-03-15 ES ES00912607T patent/ES2214257T3/es not_active Expired - Lifetime
- 2000-03-15 JP JP2000606552A patent/JP2002540089A/ja active Pending
- 2000-03-15 AT AT00912607T patent/ATE257814T1/de not_active IP Right Cessation
- 2000-03-15 WO PCT/EP2000/002282 patent/WO2000056687A1/fr active IP Right Grant
- 2000-03-15 US US09/937,389 patent/US6399841B1/en not_active Expired - Fee Related
- 2000-03-15 DE DE60007727T patent/DE60007727T2/de not_active Expired - Fee Related
- 2000-03-15 AU AU34296/00A patent/AU3429600A/en not_active Abandoned
- 2000-03-15 EP EP00912607A patent/EP1165475B1/fr not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5208398A (en) * | 1992-04-16 | 1993-05-04 | Elf Atochem N.A., Inc. | HF extraction of R365 from R141B |
EP0699649A1 (fr) * | 1994-09-05 | 1996-03-06 | SOLVAY (Société Anonyme) | Procédé pour l'hydrofluoration de chloro(fluoro)butane |
EP0905085A1 (fr) * | 1997-09-24 | 1999-03-31 | SOLVAY (Société Anonyme) | Procédé de séparation de fluorure d'hydrogène de ses mélanges avec un hydrofluoroalcane contenant de 3 à 6 atomes de carbone |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2078708A1 (fr) * | 1998-12-18 | 2009-07-15 | SOLVAY (Société Anonyme) | Compositions azéotropiques, leur utilisation et procédés de synthèse d'un hydrofluoroalcane |
US6673264B2 (en) * | 2001-06-01 | 2004-01-06 | Honeywell International Inc. | Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane and hydrogen fluoride |
US7781626B2 (en) | 2001-06-01 | 2010-08-24 | Honeywell International Inc | Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane and hydrogen fluoride |
FR2855069A1 (fr) * | 2003-05-22 | 2004-11-26 | Solvay | Procede pour la separation d'au moins un compose organique |
WO2004103514A1 (fr) * | 2003-05-22 | 2004-12-02 | Solvay (Société Anonyme) | Procede de separation d'au moins un compose organique |
Also Published As
Publication number | Publication date |
---|---|
ATE257814T1 (de) | 2004-01-15 |
ES2214257T3 (es) | 2004-09-16 |
DE60007727T2 (de) | 2004-12-02 |
JP2002540089A (ja) | 2002-11-26 |
EP1165475B1 (fr) | 2004-01-14 |
EP1165475A1 (fr) | 2002-01-02 |
AU3429600A (en) | 2000-10-09 |
DE60007727D1 (de) | 2004-02-19 |
US6399841B1 (en) | 2002-06-04 |
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