WO1997019903A1 - Production de chloro-2,2,2-trifluoroethane - Google Patents

Production de chloro-2,2,2-trifluoroethane Download PDF

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Publication number
WO1997019903A1
WO1997019903A1 PCT/GB1996/002909 GB9602909W WO9719903A1 WO 1997019903 A1 WO1997019903 A1 WO 1997019903A1 GB 9602909 W GB9602909 W GB 9602909W WO 9719903 A1 WO9719903 A1 WO 9719903A1
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WO
WIPO (PCT)
Prior art keywords
trifluoroethane
chloro
tetrafluoroethane
mixture
product stream
Prior art date
Application number
PCT/GB1996/002909
Other languages
English (en)
Inventor
David Hugh Annells
Andrew Mark Taylor
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to JP9520266A priority Critical patent/JP2000501391A/ja
Priority to AU76355/96A priority patent/AU7635596A/en
Priority to BR9611660A priority patent/BR9611660A/pt
Priority to EP96939223A priority patent/EP1021390A1/fr
Publication of WO1997019903A1 publication Critical patent/WO1997019903A1/fr

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    • 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
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • 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
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms

Definitions

  • This invention relates to the production of chloro-2,2,2-trifluoroethane, HCFC 133a, from trichloroethylene and particularly to a process for the co-production of 1,1,1, 2-tetrafluoro- ethane and chloro-2,2,2-trifluoroethane from trichloroethylene.
  • a particular embodiment of the invention relates to accessing chloro-2,2,2-trifluoroethane as a co-product from the production of 1,1,1,2-tetrafluoroethane by the two-step reaction of (i) trichloroethylene with hydrogen fluoride to form chloro-2,2,2-trifluoroethane and (ii) chloro-2,2,2-trifluoro- ethane with hydrogen fluoride to produce 1,1,1,2-tetrafluoroethane with recycle of chioro-2,2,2-trifluoroethane to step (i).
  • the two-step reaction of trichloroethylene with hydrogen fluoride in the vapour phase in the presence of a fluorination catalyst such as chromia or based on chromia to produce chloro-2,2,2-trifluoroethane and 1,1,1,2-tetrafluoroethane is well known and is the basis of a number of commercial plants for the production of 1,1,1,2-tetrafluoroethane.
  • the reaction may be carried out in a single reaction zone or the two steps ofthe reaction may be carried out in separate reaction zones.
  • the reaction produces a number of by-products, notably hydrogen chloride and various saturated and unsaturated chlorofluoro(hydro)carbons and the reaction of chloro-2,2,2-trifluoroethane to 1, 1,1,2-tetrafluoroethane is equilibrium limited so that the resulting 1, 1,1,2-tetrafluoroethane product stream usually comprises less than 20% by weight of 1, 1,1,2-tetrafluoroethane and contains major proportions of hydrogen chloride, unreacted chloro-2,2,2-trifluoroethane and hydrogen fluoride (which is commonly used in a large excess).
  • by-products notably hydrogen chloride and various saturated and unsaturated chlorofluoro(hydro)carbons
  • chloro-2,2,2-trifluoroethane to 1, 1,1,2-tetrafluoroethane is equilibrium limited so that the resulting 1, 1,1,2-tetrafluoroethane product stream usually comprises less than 20% by weight of 1, 1,1,2-tetrafluoroethane
  • the 1,1,1,2-tetrafluoroethane product stream is normally subjected to several treatments, including distillations, to recover hydrogen chloride and essentially pure 1,1,1,2-tetrafluoroethane and provide a crude recycle stream comprising mainly chloro-2,2,2-trifluoroethane and hydrogen fluoride but including various chlorofluoro(hydro)carbon by-products. Hitherto no attempt has been made to recover essentially pure chloro-2,2,2-trifluoroethane from the 1,1,1,2-tetrafluoroethane product stream as a co-product ofthe 1,1,1,2-tetrafluoroethane production process
  • the present invention resides in a process for the production of chloro-2,2,2-trifluoroethane wherein the 1,1,1 ,2-tetrafluoroethane product stream containing chloro-2,2,2-trifluoroethane and hydrogen fluoride obtained by hydrofluorination of trichloroethylene is treated to recover essentially pure chloro-2,2,2-trifluoroethane as well as essentially pure 1,1,1,2-tetrafluoroethane.
  • a process for the production of chloro-2,2,2-trifluoroethane as a co-product ofthe production of 1,1,1, 2-tetrafluoroethane by hydrofluorination of trichloroethylene which comprises (i) treating the 1,1,1,2-tetrafluoroethane product stream containing chloro-2,2,2-trifluoroethane and hydrogen fluoride to form a mixture of 1,1,1,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane and (ii) distilling said mixture to separate essentially pure chloro-2,2,2-trifluoroethane from the mixture.
  • the distillation carried out in step (ii) may be a single-stage distillation to separate chloro-2,2,2-trifluoroethane directly from the mixture or it may be a two-stage or multi- stage distillation to separate the chloro-2,2,2-trifluoroethane.
  • the single stage distillation the mixture of 1,1,1,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane formed in step (i) is fed into a distillation column and chloro-2,2,2-trifluoroethane is withdrawn directly from the column as a bottom fraction. It is to be understood that whilst this stage is described as a single-stage distillation, it may be carried out in more than one distillation column.
  • the remainder ofthe 1,1,1,2-tetrafluoroethane product stream, depleted in chloro-2,2,2-trifluoroethane, may be withdrawn as a top stream from the column and passed to further processing to recover the 1, 1,1,2-tetrafluoroethane, for example by feeding the stream back into the 1,1,1,2-tetrafluoroethane purification train ofthe production plant.
  • the top stream from the distillation column may be recycled to the distillation column to separate a further amount of chloro-2,2,2-trifluoroethane before the stream is passed to further processing to separate the 1,1,1,2-tetrafluoroethane.
  • the mixture of 1,1,1, 2-tetrafluoroethane and chloro-2,2,2-trifluoroethane formed in step (i) is essentially free from hydrogen fluoride and hydrogen chloride but will usually contain minor amounts of chlorofluorocaron by-products.
  • these by-products remain in the column and are withdrawn with the 1,1, 1,2-tetrafluoroethane stream.
  • the by-products of boiling point intermediate those of 1,1,1,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane may be withdrawn as a side stream from the column.
  • the distillation in step (ii) may be a two-stage or a multi-stage operation and a preferred distillation is a two-stage distillation in which the first stage (iia) comprises distilling the mixture of 1, 1, 1, 2-tetrafluoroethane and chloro-2,2,2-trifluoroethane formed in step (i) to separate essentially pure 1,1,1,2-tetrafluoroethane as a top fraction from the column and form a second mixture of 1,1,1,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane and the second stage (iib) comprises distilling said second mixture to separate essentially pure chloro-2,2,2-trifluoroethane as a bottom fraction and form a third mixture of 1,1,1,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane.
  • the first stage (iia) comprises distilling the mixture of 1, 1, 1, 2-tetrafluoroethane and chloro-2,2,
  • This preferred embodiment thus provides a process for the production of chloro-2,2,2-trifluoroethane as a co-product ofthe production of 1,1,1,2-tetrafluoroethane by hydrofluorination of trichloroethylene which comprises (i) treating the
  • the third mixture of 1,1,1,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane, obtained in step (iia), can be recycled to any step ofthe 1,1,1,2-tetrafluoroethane production process or to the crude 1,1,1,2-tetrafluoroethane product stream prior to step (i) ofthe process according to the invention.
  • the crude 1,1,1,2-tetrafluoroethane product stream fed to step (i) ofthe process preferably is essentially free from hydrogen chloride
  • the process ofthe invention thus preferably includes an additional step of treating the crude product stream, for example by distillation, to separate hydrogen chloride prior to treatment according to step (i)
  • a mixture of 1,1,1,2-tetrafluoroethane, chloro-2,2,2-trifluoroethane and hydrogen fluoride may be crudely separated from the 1,1,1,2-tetrafluoroethane product stream, for instance as the top stream from a distillation column, from a mixture comprising mainly chloro-2,2,2-trifluoroethane and hydrogen fluoride, for example a liquid bottom stream and/or a gaseous side stream from the distillation cloumn
  • the chloro-2,2,2-trifluoroethane/hydrogen fluoride mixture is preferably recycled to the 1,1,1,2-tetrafluoroethane production process, in the case of a two step process either to the chloro-2,2,2-trifluoroethane conversion step or to the trichloroethylene conversion step
  • Distillation ofthe 1,1,1,2-tetrafluoroethane product stream, after removal of hydrogen chloride, to separate a mixture of 1,1,1, 2-tetrafluoroethane and hydrogen fluoride from a recycle stream comprising mainly chloro-2,2,2-trifluoroethane and hydrogen fluoride is a conventional step in the production of 1 , 1 , 1 ,2-tetrafluoroethane
  • the distillation is fairly crude so that in the conventional distillation the separated mixture of 1,1,1,2-tetrafluoroethane and hydrogen fluoride may contain chloro-2,2,2-trifluoroethane which is removed at a later stage and recycled to the 1,1,1,2-tetrafluoroethane production process.
  • the conventional distillation is operated under conditions (temperature and pressure) designed to mudirnise the carry over of chloro-2,2,2-trifluoroethane with the 1,1,1,2-tetrafluoroethane and hydrogen fluoride so as to reduce the burden on the subsequent separation step
  • the treatment according to step (i) ofthe invention is operated under conditions, for example distillation under higher temperature and/or lower pressure, wherby an appreciable amount of chloro-2,2,2-trifluoroethane is present in the separated mixture so as to provide a source of chloro-2,2,2-trifluoroethane for recovery as a co-product ofthe 1, 1,1,2-tetrafluoroethane production process
  • the amount of chloro-2,2,2-trifluoroethane in the mixture separated in step (i) and hence the amount of chloro-2,2,2-trifluoroethane accessable as a co-product is dependent upon and therefor controlled by the operating conditions ofthe distillation column.
  • the column will usually be operated at a pressure in the range of about 10 barg to 20 barg
  • the mixture of 1,1,1,2-tetrafluoroethane, chloro-2,2,2-trifluoroethane and hydrogen fluoride separated from the product stream is then treated to remove the hydrogen fluoride and form a mixture of 1 , 1 , 1 ,2-tetrafluoroethane and chloro-2,2,2-trifluoroethane.
  • the removal of hydrogen fluoride may be effected by any suitable technique, for example by scrubbing the mixture with water or an alkaline solution.
  • step (i) usually comprises crude distillation ofthe 1,1,1,2-tetrafluoroethane product stream to separate a mixture of 1,1,1,2-tetrafluoroethane, chloro-2,2,2-trifluoroethane and hydrogen fluoride.
  • the 1,1,1,2-tetrafluoroethane product stream usually contains several other chlorofluoro(hydro)carbon components and these will divide on the basis of "lights” and "heavies” between the mixtures separated in step (i)
  • the mixture obtained in step (i) may contain one or more of these "lights” components and is usually treated, for example by distillation, to remove these components prior to feeding to step (ii).
  • the "lights” components removed in this treatment are generally unsuitable for recycle to the 1,1,1,2-tetrafluoroethane production process and so may be vented and disposed of for example in a thermal oxidiser.
  • the operating conditions for "lights"components separation are known and/or readily determined but as a guide the conditions will usually be a column pressure of from about 10 barg to 20 barg
  • step (ii) ofthe process Essentially pure chloro-2,2,2-trtifluoroethane is separated in step (ii) ofthe process.
  • 1,1,1,2-tetrafluoroethane is separated by distillation in step (iia) from a second mixture of chloro-2,2,2-trifluoroethane and a small amount of 1,1, 1,2-tetrafluoroethane, the latter mixture then being distilled in step (iib) to separate essentially pure chloro-2,2,2-trifluoroethane for recovery.
  • the operating conditions for the distillation columns are readily determined by the operator but as a guide the conditions will usually be a column pressure of from about 1 barg to 15 barg, say 5 to 12 barg in step (iia) and a column pressure of about 1 barg to 10 barg in step (iib).
  • any residual (third) mixture of 1,1, 1,2 -tetrafluoroethane and chloro-2,2,2-trifluoroethane from step (iib) may be recycled for further treatment to recover the product values, for example by recycle to the 1,1,1,2-tetrafluoroethane product stream from the 1,1,1,2-tetrafluoroethane production process or to any step ofthe product separation treatment or to any step ofthe 1,1,1,2-production process.
  • the 1,1,1,2-tetrafluoroethane product stream may be the product stream from any process for the production of 1,1,1,2-tetrafluoroethane by hydrofluorination of trichloroethylene and the invention is not restricted to any particular process for producing 1,1,1,2-tetrafluoroethane from trichloroethylene.
  • the process according to the invention may be operated as a batch process although we prefer continuous operation.
  • continuous operation at least up to and including step (iia).
  • Step (iib) may be included in the continuous operation but if desired the second mixture of chloro-2,2,2-trifluoroethane and 1,1,1,2- tetrafluoroethane from step (iia) may be stockpiled and treated separately as a batchwise operation in step (iib).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de production de chloro-2,2,2-trifluoroéthane comme coproduit de la production de 1,1,1,2-tétrafluoroéthane par hydrofluoruration de trichloroéthylène consistant à: (i) traiter un flux de 1,1,1,2-tétrafluoroéthane contenant du chloro-2,2,2-trifluoroéthane et du fluorure d'hydrogène de manière à former un mélange de 1,1,1,2-tétrafluoroéthane et de chloro-2,2,2-trifluoroéthane; (ii) distiller ledit mélange pour en extraire du chloro-2,2,2-trifluoroéthane pratiquement pur. Le type de distillation préféré de l'étape (ii) consiste à: (iia) distiller le mélange pour en extraire le 1,1,1,2-tétrafluoroéthane pratiquement pur et former un deuxième mélange de 1,1,1,2-tétrafluoroéthane et de chloro-2,2,2-trifluoroéthane; et (iib) distiller ce deuxième mélange pour en extraire du chloro-2,2,2-trifluoroéthane pratiquement pur.
PCT/GB1996/002909 1995-11-28 1996-11-26 Production de chloro-2,2,2-trifluoroethane WO1997019903A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP9520266A JP2000501391A (ja) 1995-11-28 1996-11-26 クロロ―２，２，２―トリフルオロエタンの製造
AU76355/96A AU7635596A (en) 1995-11-28 1996-11-26 Production of chloro-2,2,2-trifluoroethane
BR9611660A BR9611660A (pt) 1995-11-28 1996-11-26 Processo para a produção de cloro-2,2,2-trifluoroetano
EP96939223A EP1021390A1 (fr) 1995-11-28 1996-11-26 Production de chloro-2,2,2-trifluoroethane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9524268.1 1995-11-28
GBGB9524268.1A GB9524268D0 (en) 1995-11-28 1995-11-28 Production of chloro-2,2,2-trifluoroethane

Publications (1)

Publication Number Publication Date
WO1997019903A1 true WO1997019903A1 (fr) 1997-06-05

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Application Number Title Priority Date Filing Date
PCT/GB1996/002909 WO1997019903A1 (fr) 1995-11-28 1996-11-26 Production de chloro-2,2,2-trifluoroethane

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EP (1) EP1021390A1 (fr)
JP (1) JP2000501391A (fr)
CN (1) CN1207723A (fr)
AU (1) AU7635596A (fr)
BR (1) BR9611660A (fr)
CA (1) CA2238508A1 (fr)
GB (1) GB9524268D0 (fr)
MX (1) MX9804231A (fr)
WO (1) WO1997019903A1 (fr)

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CN112250540B (zh) * 2020-10-14 2023-10-31 太仓中化环保化工有限公司 一种从精馏重组分中分离R134a、R133a和R124的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5276223A (en) * 1992-08-10 1994-01-04 Showa Denko Kabushiki Kaisha Process for producing 1,1,1,2-tetrafluoroethane
EP0582156A1 (fr) * 1992-08-05 1994-02-09 Showa Denko Kabushiki Kaisha Procédé de préparation du 1,1,1,2-tétrafluoroéthane
JPH0640963A (ja) * 1992-07-27 1994-02-15 Showa Denko Kk １，１，１，２テトラフルオロエタンの製造法
JPH0640962A (ja) * 1992-07-27 1994-02-15 Showa Denko Kk １，１，１，２テトラフルオロエタンの製法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0640963A (ja) * 1992-07-27 1994-02-15 Showa Denko Kk １，１，１，２テトラフルオロエタンの製造法
JPH0640962A (ja) * 1992-07-27 1994-02-15 Showa Denko Kk １，１，１，２テトラフルオロエタンの製法
EP0582156A1 (fr) * 1992-08-05 1994-02-09 Showa Denko Kabushiki Kaisha Procédé de préparation du 1,1,1,2-tétrafluoroéthane
US5276223A (en) * 1992-08-10 1994-01-04 Showa Denko Kabushiki Kaisha Process for producing 1,1,1,2-tetrafluoroethane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9411, Derwent World Patents Index; Class E16, AN 94-089295, XP002023477 *
DATABASE WPI Section Ch Week 9411, Derwent World Patents Index; Class E16, AN 94-089296, XP002023476 *

Also Published As

Publication number Publication date
JP2000501391A (ja) 2000-02-08
CN1207723A (zh) 1999-02-10
CA2238508A1 (fr) 1997-06-05
EP1021390A1 (fr) 2000-07-26
AU7635596A (en) 1997-06-19
GB9524268D0 (en) 1996-01-31
MX9804231A (es) 1998-09-30
BR9611660A (pt) 1999-02-23

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