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WO2002002492A2 - Procede de preparation de pentafluoroethane - Google Patents

Procede de preparation de pentafluoroethane Download PDF

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Publication number
WO2002002492A2
WO2002002492A2 PCT/US2001/020442 US0120442W WO0202492A2 WO 2002002492 A2 WO2002002492 A2 WO 2002002492A2 US 0120442 W US0120442 W US 0120442W WO 0202492 A2 WO0202492 A2 WO 0202492A2
Authority
WO
WIPO (PCT)
Prior art keywords
hcfc
reaction
reaction product
hfc
train
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.)
Ceased
Application number
PCT/US2001/020442
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English (en)
Other versions
WO2002002492A3 (fr
Inventor
Gustavo Cerri
Rajat S. Basu
Jeffrey Charles Richards
Jason Thomas Stuck
Hsueh Sung Tung
Jay Bradley Patty
Stephen Alan Cottrell
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.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
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 Honeywell International Inc filed Critical Honeywell International Inc
Priority to AU2001271524A priority Critical patent/AU2001271524A1/en
Publication of WO2002002492A2 publication Critical patent/WO2002002492A2/fr
Publication of WO2002002492A3 publication Critical patent/WO2002002492A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to processes for preparing halogenated ethanes, and particularly pentafiuoroethane.
  • Hydrofluorocarbons in general, and pentafiuoroethane (herein referred to as HFC-125) in particular, are of particular interest as replacements for environmentally disadvantageous chlorofluorocarbons (CFCs), which heretofore frequently have been used, for example, in air conditioning and refrigeration applications.
  • CFCs chlorofluorocarbons
  • HFCs do not contain chlorine and therefore do not decompose to form chlorine-containing chemical species, which are suspected of causing depletion of the ozone layer. While HFCs thus avoid the main disadvantage of such chlorine- containing compounds, they nevertheless possess many of the beneficial properties of those compounds.
  • HFCs have been used successfully in place of HCFCs and CFCs as heat transfer agents, blowing agents and propellants.
  • HFCs are desirable targets of chemical synthesis. It is known to manufacture pentafiuoroethane by reacting perchloroethylene (PCE) and excessive hydrogen fluoride (HF) in the gas phase in the presence of a fluorination catalyst. This reaction generally yields a variety of reaction products in addition to HFC-125, several of which are undesirable chlorinated compounds. Particularly disadvantageous byproducts include trichlortrifluoroethane (CFC-113 and CFC-113a),
  • CFC-115 in particular, has a relatively high ozone degradation potential (ODP) and
  • HCFC 123/123a chlorotetrafluoroethane
  • HCFC 124/124a chlorotrifluoroethane
  • chlorotetrafluoroethane (HCFC- 124/ 124a) is frequently recycled to the
  • CFC-115 is a compound that is not readily converted
  • CFC-114/114a are generally converted to CFC-115 in the fluorination reaction, and
  • HFCs particularly HFC-125
  • HCFCs to the undesired
  • Fig. 1 is a generalized process flow diagram illustrating one embodiment of the
  • Fig. 2 is a generalized process flow diagram illustrating a second embodiment of the
  • FIG. 3 is a generalized process flow diagram illustrating a third embodiment of the processes of the present invention.
  • Fig. 4 is a generalized process flow diagram illustrating a fourth embodiment of the processes of the present invention.
  • Fig. 5 is a generalized process flow diagram illustrating a fifth embodiment of the processes of the present invention.
  • Fig. 6 is a generalized process flow diagram illustrating a fluorination process which uses a single reaction train.
  • HCFC-124 shall refer to HCFC-124, its isomer HCFC-124a, and mixtures of these.
  • HCFC- 123 refers to HCFC-123, its isomers HCFC-123a and HCFC-123b, and mixtures of these
  • CFC-114" shall refer to CFC-114, its isomer CFC-114a, and mixtures of these.
  • the reaction product of the first train will also include at least (HFC-125) and (CFC-115).
  • the first reaction train may be operated in certain embodiments to maximize the production of HFC-125. Furthermore, it is contemplated that such embodiments will be preferred when it is desired to maximize the yield of HFC-125 and
  • the first reaction train will be operated to maximize the production of
  • reaction train refers to one or more reaction zones
  • vessels each defining a separate reaction zone, connected by appropriate conduits and
  • reaction train can thus contain a single reaction chamber or zone, but in
  • reaction train contains two or more chambers and/or zones
  • zone is fed, at least partially but preferably substantially completely, to a second reaction chamber or zone.
  • HFC-121 HCFC-121
  • HCFC-122 HCFC-122
  • HCFC-123 HCFC-124
  • HFC-125 which is a desired
  • reaction train results in a process that is improved in several respects.
  • the reaction train results in a process that is improved in several respects.
  • HCFCs and HFCs's in general and HFC-125 in particular.
  • the HFC-125:CFC-115 ratio (on a weight basis) is at least about
  • the average reaction temperatures in the second train of the present invention are higher than the average reaction temperatures in the first train, and even more preferably at least about 20 to about 50°F higher than the average reaction temperatures in the first train.
  • the preferred embodiments of the present invention utilize a process flow pattern as illustrated schematically in Fig. 1. More particularly, the processes of the present invention preferably utilize a first reaction train Rl, a second reaction train R2, and separation means S3.
  • the first reaction train Rl receives PCE and HF, preferably by feed streams 10 and 20, respectively.
  • the first reaction train preferably also receives a recycle of products produced in the first and/or second reaction train, preferably by recycle stream 90.
  • the fresh feed streams 10 and 20 and the recycle stream 90 are fluorinated in the reaction train Rl to produce a final reaction product 30.
  • the second reaction train R2 receives recycled HCFC- 124, preferably via feed stream 50, and fresh or recycled HF, preferably via feed stream 40.
  • the second reaction train R2 produces a second final reaction product stream 60.
  • the first reaction train produces a final reaction
  • product stream containing CFCs, HCFCs and HFCs, and more particularly at least HFC-125,
  • final reaction product stream means a
  • HCFC-124 preferably HCFC-124
  • recycle stream 50 preferably HCFC-124
  • This second reaction train also preferably
  • each of the reaction trains of the present invention can be any of the reaction trains of the present invention. It is contemplated that each of the reaction trains of the present invention.
  • first and second reaction trains each preferably comprise one or more reaction
  • the amount of the fluorination catalyst used can be any fluorination catalyst.
  • HF:organics of at least about 5:1, and even more preferably of from
  • the first final reaction product stream 30, which generally will contain a mixture of
  • the separation step of the present invention produces at least one stream 50
  • stream 50 which is the recycle stream or streams to the second reaction train(s), contains
  • HCFC-124 in an amount that is at least about 25%, more preferably at least about 50 %, and
  • S3 also produces one or more streams containing desired products, including an HFC-125
  • the streams 90 can be sent for further
  • the first reaction train can comprise a single reaction zone or
  • first reaction train Rl in accordance with the present invention are illustrated in Figs. 2 - 5.
  • the primary reactant feeds to the first reaction train are PCE stream 10 and HF stream 20.
  • the first reaction train also receives one or more recycle feed
  • recycle stream 90 The amount and composition of recycle stream 90 can vary widely within the
  • reaction train Rl include only a minor proportion of the HCFC-124 produced by the
  • the first reaction train is less than about 10% by weight of the HCFC produced by the
  • the first reaction train Rl can comprise a single reaction zone, it is generally preferred
  • first reaction train comprise at least two reaction zones, with the first zone Zl 1 in the
  • second reaction zone also receives additional fresh feed or additional recycle feed, such a fresh PCE stream 10, and/or additional fresh HF, which is combined with the effluent 22
  • zone Zl 1 in mixing valve V2 and then introduced as a mixed stream 23 into zone Z12.
  • the effluent from the second zone can constitute the final reaction product 30 from the first
  • reaction train Rl as illustrated in Figs 2 - 4, or some or all of the effluent stream 22 can be
  • reaction train configuration As illustrated by the foregoing, numerous variations on reaction train configuration
  • the fluorination reaction in the first train comprises a vapor phase reaction
  • Such operating parameters include temperature, mole ratio of organics, and
  • contact or residence time See, for example, Tung, et al, U.S. Patent No.
  • HFC-125 is a desired end product. Therefore, according to many embodiments the various
  • operating parameters including temperature, mole ratio and contact time, are preferably
  • the first reaction train can be adjusted so that HFC-125 preferably comprises at least about 25
  • operating parameters of the first reaction train can be adjusted so that HFC- 124 preferably
  • the present invention provides a second, parallel reaction train whose primary purpose is to
  • present invention to accommodate differing sets of operational priorities.
  • the reaction of PCE with HF preferably is
  • phase in each reaction zone is preferably conducted at temperatures of from about 550°F to
  • reaction is carried out over a fluorination catalyst
  • chromium oxyfluoride formed by the partial fluorination of chromium
  • the second reaction train can comprise a single reaction zone or multiple zones
  • the primary reactant feeds to the second reaction train are HF stream 40 and recycle stream 50.
  • recycle stream 50 can vary widely within the scope hereof,
  • recycle stream(s) 50 which are introduced to the reaction train R2 include an amount of
  • streams 40 and 50 to the reaction train can be used, it is preferred that these streams are first
  • the feed streams are introduced to a means for mixing the streams, such a mixing valve V3.
  • the feed streams are
  • the second reaction train R2 can comprise a single reaction zone, it is generally preferred
  • the second reaction train comprise at least two reaction zones, with the first zone Z21
  • the effluent from the second zone can constitute the final reaction product 60, as
  • the effluent from this zone comprises the
  • the vapor phase in each reaction zone is preferably conducted at temperatures of from about
  • reaction is carried out over a
  • fluorination catalyst such as, for example, chromium-based or other suitable catalysts, such as
  • HF to the reactive organic components in the feed to the second reaction zone is at least about
  • organics such as HCFC- 123 are recycled in one or more streams.
  • organics such as HCFC- 123
  • recycle streams can-be recycled to one or more zones in the first reaction train and/or to
  • the HFC 125 is typically withdrawn together with CFC-115 as a purified product.
  • the H CFC-124 in the product can also be isolated to
  • HFC-124 varying degrees of purity to form an HFC-124 recycle stream.
  • HFC-124 such HFC-124
  • recycle can include other components according to any of the known separation processes,
  • the single reaction train has a first reaction zone comprising a first reaction vessel Zl
  • reaction vessel Z2 is charged with a first reaction vessel Z1 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a first reaction vessel Z2 and a second reaction vessel Z2 connected in series. Each reaction vessel is charged with a
  • fresh perchloroethylene feed stream 10 is preheated to a temperature of about 560°F and then
  • a first recycle stream 90a at a temperature of 560°F and a
  • the contact time in the first reaction zone is
  • the effluent from the first reaction zone is heated to a temperature of about 650 °F, mixed with a second recycle stream 90b and then introduced into the second reaction zone
  • the second reaction zone is operated at a pressure of about 115 psig.
  • the second reaction zone is about 9 seconds.
  • the same catalyst as used in Example Cl is used. Moreover, the same amount of catalyst is used, with the catalyst volume being divided substantially equally among the four reaction zones.
  • the first reaction train Rl has a first reaction zone Zl comprising a vessel charged with the above noted catalyst. A fresh PCE and HF are introduced together as a fresh feed stream preheated to a temperature of about 560°F. A first recycle stream at a temperature of
  • the mole ratio of HF:organics in the feed (including the recycle stream) is held at about 15.
  • the reaction is conducted at a pressure of about 145 psig.
  • reaction zone is about 12 seconds.
  • the effluent from the first reaction zone in the first reaction train is heated to a temperature of about 650 °F, mixed with a second recycle stream and then introduced into a second reaction zone Z12.
  • the reaction in the second zone is conducted at a pressure of about 145 psig.
  • the contact time in the second reaction zone is about 12 seconds.
  • the second reaction train also has a first reaction zone Z21 comprising the first zone
  • Z21 in the second train R2 is feed with a fresh HF stream and HCFC-124 recycled from the
  • the HF is preheated to a temperature of about 580°F and then introduced
  • the reaction is held at about 15.
  • the reaction is conducted at a pressure of about 112 psig.
  • the contact is conducted at a pressure of about 112 psig.
  • time in the first reaction zone Z21 is about 65 seconds.
  • reaction zone Z22 introduced into a second reaction zone Z22.
  • the reaction is conducted at a pressure of about
  • the contact time in the second reaction zone is about 65 seconds.
  • a comparison of Examples Cl and 1 reveals that, for the same amount of catalyst and substantially the same amount of fresli feedstock, the process of the present invention is capable of providing a substantial improvement in selectivity and in the ratio of the desired to the less desired components. More particularly, the selectivity of HFC-125 is about 27% (on a relative basis) greater than for a single reaction train embodiment, while the HFC-125/CFC- 115 ratio is improved by about 52%.

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

Abstract

L'invention concerne un procédé permettant d'obtenir une sélectivité améliorée du HFC-125 et/ou un rapport HFC/HCFC (et en particulier un rapport HFC-125/CFC-115) amélioré, grâce à un traitement de fluoration consistant à faire réagir du PCE et du fluorure d'hydrogène (HF) au cours d'une première chaîne de réactions afin d'obtenir un produit réactionnel comprenant au moins un (HCFC-124), et à séparer de ce produit réactionnel au moins une partie du HCFC-124, et à faire réagir le HCFC-124 ainsi séparé avec du HF au cours d'une seconde chaîne de réactions afin d'obtenir un second produit réactionnel contenant au moins du HFC-125.
PCT/US2001/020442 2000-06-30 2001-06-27 Procede de preparation de pentafluoroethane Ceased WO2002002492A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001271524A AU2001271524A1 (en) 2000-06-30 2001-06-27 Process for the preparation of pentafluoroethane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60853900A 2000-06-30 2000-06-30
US09/608,539 2000-06-30

Publications (2)

Publication Number Publication Date
WO2002002492A2 true WO2002002492A2 (fr) 2002-01-10
WO2002002492A3 WO2002002492A3 (fr) 2002-05-16

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PCT/US2001/020442 Ceased WO2002002492A2 (fr) 2000-06-30 2001-06-27 Procede de preparation de pentafluoroethane

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AU (1) AU2001271524A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557444A (zh) * 2014-12-03 2015-04-29 嵊州领航信息科技有限公司 一种制备hfc-125的系统和方法
JP2018511633A (ja) * 2015-04-14 2018-04-26 アルケマ フランス ペンタフルオロエタンの精製方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020441A1 (fr) * 1993-03-05 1994-09-15 Daikin Industries, Ltd. Procede de production de 1,1,1,2,2-pentafluoroethane, procede de production de 2,2-dichloro-1,1,1-trifluoroethane, et procede de purification de 1,1,1,2,2-pentafluoroethane
GB9325756D0 (en) * 1993-12-16 1994-02-16 Ici Plc Production of pentafluoroethane
GB9406813D0 (en) * 1994-04-06 1994-05-25 Ici Plc Production of pentafluoroethane
JP3628349B2 (ja) * 1994-05-27 2005-03-09 昭和電工株式会社 １，１，１，２，２−ペンタフルオロエタンの製法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557444A (zh) * 2014-12-03 2015-04-29 嵊州领航信息科技有限公司 一种制备hfc-125的系统和方法
JP2018511633A (ja) * 2015-04-14 2018-04-26 アルケマ フランス ペンタフルオロエタンの精製方法

Also Published As

Publication number Publication date
AU2001271524A1 (en) 2002-01-14
WO2002002492A3 (fr) 2002-05-16

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