US007230l46B2
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`(12) United States Patent
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`Merkel et al.
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`(10) Patent No.:
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`(45) Date of Patent:
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`US 7,230,146 B2
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`*Jun. 12, 2007
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`8/2005 Janssens et al.
`2005/0171391 A1
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`FOREIGN PATENT DOCUMENTS
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`0522639
`1/1993
`0644173
`3/1995
`0 974 571 A2
`1/2000
`
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`
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`094571
`1/2000
`10007604
`1/1998
`11140002
`5/1999
`2000169404
`6/2000
`W0 9504021
`2/1995
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`WO/96/01797 A
`1/1996
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`WO98/33755
`8/1998
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`WO 2005/012212
`2/2005
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`WO2005/012212
`2/2005
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`WO2005/042451 A
`5/2005
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`OTHER PUBLICATIONS
`
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`Henne et al., “Fluorinated Derivatives of Propane and Propylene
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`VI,” J. Am. Chem. Soc., 68, 496-497 (1946).
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`Tarrant, et al., “Free Radical Additions Involving Fluorine Com-
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`IV. The Addition of Dibromodifluoromethane to Some
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`Fluorooolefins,” J. Am. Chem Soc., 77, 2783-2786 (1955).
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`Kimura, et al., “Poly(ethylene glycols) and poly(ethylene glycol)-
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`copolymers
`extraordinary
`catalysts
`are
`grafted
`for
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`dehydrohalogenation under two-phase and three-phase conditions,”
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`J. Org. Chem., 48, 195-0198 (1983).
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`Knunyants I L et al. “Reactions OfFluoro Olefins Communication
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`13. Catab/tic Hydrogenation OfPeifiuoro Olefins”, Bulletin Of The
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`Academy Of Sciences Of The USSR,
`pp.
`1312-1317,
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`XP000578879.
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`Database WPI, Section CH, Week 199812, Derwent Publications
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`LTD., London, GB; AN 1998-126109, XP002324078.
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`Database WPI, Section CH, Week 199931, Derwent Publications
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`LTD., London, GB; AN 1999-367023, XP002324079.
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`PCT Search Report Form PCT/ISN206 for PCT/US2004/035131
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`Filed Oct. 25, 2004.
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`Knunyants I. L. et al: “Reactions of Fluoro Olefins Communication
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`13, Catalytic Hydrogenation of Perfluoro Olefins” Bulletin of Acad-
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`emy ofSciences ofthe USSR, Division ofChemical Sciences, 1960,
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`pp. 1312-1317, XP000578879; ISSN: 0568-5230, p. 1313, (XI)->
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`(XIII) p. 1316, paragraph 6.
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`Knunyants I L et al. “Reactions OfFluoro Olefins Communication
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`13. Catab/tic Hydrogenation OfPeifiuoro Olefins”, Bulletin Of The
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`Academy Of Sciences ofthe USSR, pp. 1312-1317, XP000578879,
`
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`1960.
`
`Zhuranl Organicheskoi Khimii, 28(4), 672-80, (1982).
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`Free-radical additions to unsaturated systems, Journal of Chemical
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`Society, Section C: Organic, (3), 414-21, p. 415, 1970.
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`XP000578879, Bulletin of the Academy of Sciences of the USSR,
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`Division of Chemical Sciences- ISSN 0568-5230, p. 1312-1317,
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`1960.
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`EP
`EP
`EP
`EP
`JP
`JP
`JP
`W0
`WO
`WO
`W0
`WO
`WO
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`* cited by examiner
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`Primary Examiner—Sikarl A. Witherspoon
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`(57)
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`ABSTRACT
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`Dehydrohalogenation processes for the preparation of fluo-
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`ropropenes from corresponding halopropanes, in which the
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`fluoropropenes have the formula CF3CY=CXNHP, wherein
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`X and Y are independently hydrogen or a halogen selected
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`from fluorine, chlorine, bromine and iodine; and N and P are
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`independently integers equal to 0,
`1 or 2, provided that
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`(N+P):2.
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`76 Claims, No Drawings
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`(54) PROCESS FOR PRODUCING
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`FLUOROPROPENES
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`(75)
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`Inventors: Daniel C. Merkel, West Seneca, NY
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`(US); Rajiv R. Singh, Getzville, NY
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`(US); Hsueh Sung Tung, Getzville, NY
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`(US)
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`(73) Assignee: Honeywell International Inc.,
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`Morristown, NJ (US)
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`( * ) Notice:
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`Subject to any disclaimer, the term of this
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`patent is extended or adjusted under 35
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`U.S.C. l54(b) by 0 days.
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`This patent is subject to a terminal dis-
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`claimer.
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`(21) Appl. No.: 10/694,272
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`(22)
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`(65)
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`Filed:
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`Oct. 27, 2003
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`Prior Publication Data
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`US 2005/0090698 A1
`Apr. 28, 2005
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`(51)
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`Int. Cl.
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`C07C 17/25
`(2006.01)
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`(52) U.S. Cl.
`.................... .. 570/155; 570/157; 570/164;
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`570/166; 570/167; 570/168; 570/179
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`(58) Field of Classification Search .............. .. 570/155,
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`570/157, 164, 166, 167, 168, 179
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`See application file for complete search history.
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`(56)
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`References Cited
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`U.S. PATENT DOCUMENTS
`
`
`
`.............. .. 260/653.4
`6/1959 Ruh et al.
`
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`8/1961 Rausch et al.
`
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`10/1969 Potts et al.
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`4/1972 Regan ...................... .. 424/350
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`8/1984 Zimmer et al.
`........... .. 502/169
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`3/1987 Woodard et al.
`
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`1/1989 Baizer et al.
`............. .. 502/228
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`2/1990 Ihara et al.
`
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`
`............... .. 502/228
`10/1992 Tung et al.
`
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`7/1996 Van Der Puy et al.
`570/167
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`8/1996 Morikawa et al.
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`11/1996 Van Der Puy et al.
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`10/1997 Aoyama et al.
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`1/1998 Tung ........................ .. 570/166
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`3/1998 Van Der Puy et al.
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`10/1999 Thenappan et al.
`....... .. 570/167
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`11/1999 Van Der Puy ............ .. 570/175
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`2/2000 Thenappan et al.
`....... .. 570/188
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`2/2000 Mallikarjuna et al.
`.... .. 570/136
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`8/2000 Sakyu et al.
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`9/2000 Elsheikh et al.
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`4/2002 Nappa et al.
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`4/2003 Nair et al.
`................ .. 570/157
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`10/2004 Pennetreau et al.
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`10/2005 Nair et al.
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`1/2005 Tung et al.
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`4/2005 Merkel et al.
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`2,889,379 A
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`2,996,555 A
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`3,472,826 A
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`3,659,023 A
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`4,465,786 A
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`4,650,914 A
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`4,798,818 A
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`4,900,874 A
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`5,155,082 A
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`5,532,419 A
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`5,545,777 A
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`5,574,192 A
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`5,679,875 A
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`5,710,352 A
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`5,728,904 A
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`5,969,198 A
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`5,986,151 A
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`6,023,004 A
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`6,031,141 A
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`6,111,150 A
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`6,124,510 A *
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`6,369,284 B1
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`6,548,719 B1
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`6,809,226 B1
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`6,958,424 B1
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`2005/0020862 A1
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`2005/0090698 A1
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`570/167
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`.......... .. 570/156
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`Page 1 of 8
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`Arkema Exhibit 1020
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`Arkema Exhibit 1020
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`Page 1 of 8
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`

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`US 7,230,146 B2
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`1
`PROCESS FOR PRODUCING
`
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`FLUOROPROPENES
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`
`
`BACKGROUND OF THE INVENTION
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`2
`SUMMARY OF THE INVENTION
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`The present invention provides two new dehydrohaloge-
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`nation methods by which fluoropropenes may be commer-
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`cially produced with high yield and selectivity. According to
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`one aspect of the present invention, a dehydrohalogenation
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`process is provided for the preparation of fluoropropenes of
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`the formula CF3CY=CXNHP wherein X and Y are inde-
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`pendently hydrogen or a halogen selected from the fluorine,
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`chlorine, bromine and iodine, and N and P are independently
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`integers equal to 0, 1 or 2, provided that (N+P):2, in which
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`there is reacted, without a catalyst, a halopropane of the
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`formula:
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`CFSC
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`wherein R1, R2, X and Y are independently hydrogen or a
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`halogen selected from fluorine, chlorine, bromine and
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`iodine, provided that at least one of R1, R2, X and Y is a
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`halogen and there is at least one hydrogen and one halogen
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`on adjacent carbon atoms; with a solution of at least one
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`alkali or alkaline earth metal hydroxide in a non-aqueous,
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`non-alcohol solvent therefor that is at least essentially mis-
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`cible with the halopropane, wherein the reaction is per-
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`formed at a temperature at which dehydrohalogenation will
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`occur.
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`Reactions performed without a catalyst produce cleaner
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`reaction products, thereby simplifying product work-up and
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`isolation. The halopropane can be CF3CH2CF2H (a com-
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`mercially available compound also known as HFC-245fa) or
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`CF3CH2CHClF (HCFC-244fa) a by-product of the manu-
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`facture of HFC-245fa. Both halopropanes will dehydroha-
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`logenate to form HFC-1234ze.
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`According to another aspect of the present invention, a
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`dehydrohalogenation process is provided for the preparation
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`of fluoropropenes of the formula CF3CY=CXNHP, wherein
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`X and Y are independently hydrogen or a halogen selected
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`from fluorine, chlorine, bromine and iodine, and N and P are
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`independently integers equal
`to 0,
`1 or 2 provided that
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`(N+P):2, comprising heating to a temperature at which
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`dehydrohalogenation by thermal decomposition occurs a
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`halopropane of the formula:
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`CF3C(YR1)C(XNHPR2)
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`wherein R1, R2, X and Y are independently hydrogen or a
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`halogen selected from fluorine, chlorine, bromine and
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`iodine, provided that at least one of R1, R2, X and Y is a
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`halogen and there is at least one hydrogen and one halogen
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`on adjacent carbon atoms. The thermal decomposition reac-
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`tion can be performed either with or without a catalyst for
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`hydrogen halide removal, such as transition metal halides
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`and oxides and combination thereof, preferably iron halides,
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`nickel halides, cobalt halides and combinations thereof.
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`HFC-245fa and CF3CH2CHClF (HCFC-244fa) can also be
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`reacted by the thermal decomposition reaction of the present
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`invention to form HFC-1234ze.
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`DETAILED DESCRIPTION OF THE
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`INVENTION
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`The present invention can be generally described as a
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`process for the preparation of fluoropropenes of the formula
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`CF3CY=CXNHP wherein X and Y are independently a
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`hydrogen or a halogen selected from fluorine, chlorine,
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`bromine and iodine; and N and P are integers independently
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`equal to 0, 1 or 2, provided that (N+P):2.
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`Two dehydrohalogenation methods by which the fluoro-
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`propenes may be prepared are disclosed.
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`10
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`45
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`60
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`65
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`The present invention relates to a process for producing
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`fluoropropenes in good yield on an industrial scale using
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`commercially and readily available starting materials. More
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`particularly, the present invention relates to a process for
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`producing fluoropropenes by the dehydrohalogenation of
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`halopropanes, either by reaction with an essentially miscible
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`alkali or alkaline earth metal hydroxide solution in a non-
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`alcohol solvent, or by thermal decomposition.
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`The production of fluoropropenes such as CF3CH=CH2
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`by catalytic vapor phase fluorination of various saturated
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`is
`and unsaturated halogen-containing C3
`compounds
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`described in U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,
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`786. U.S. Pat. No. 5,532,419 discloses a vapor phase cata-
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`lytic process for the preparation of fluoroalkene using a
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`chloro- or bromo-halofluorocarbon and HF. EP 974,571
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`discloses the preparation of 1,1,1,3-tetrafluoropropene by
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`contacting 1,1,1,3,3-pentafluoropropane (HFC-245fa) in the
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`vapor phase with a chromium-based catalyst at elevated
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`temperature, or in the liquid phase with an alcoholic solution
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`of KOH, NaOH, Ca(OH)2 or Mg(OH)2.
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`A fluoropropene of particular interest is 1,3,3,3-tetrafluo-
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`ropropene (HFC-1234ze), which has potential use as a low
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`global warming potential refrigerant. However, this material
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`is presently not available in commercial quantity. The exist-
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`ing technology to make HFC-1234ze is a fluorination pro-
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`cess using 1,1,1,3,3-pentachloropropane (HCC-240fa) and
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`HF in the presence of a vapor phase catalyst. HFC-1234ze
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`is a by-product of the reaction that is made in relatively
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`small quantity,
`i.e.,
`less than about 8 area % in a gas
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`chromatograph (GC) of the organic reaction product.
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`The process is very expensive because of the low selec-
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`tivity for the desired product, HFC-1234ze. The reaction is
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`actually intended for the manufacture of HFC-245fa,
`in
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`which small quantities of HFC-1234ze is produced as a
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`by-product. Complicating matters, the process involves han-
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`dling large quantities of hazardous materials such as HF and
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`HCl.
`
`Henne et al., J. Am. Chem. Soc., 68, 496—497 (1946)
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`described the synthesis of various fluoropropenes from
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`CF3CH2CF3 using, e.g., alcoholic KOH, with varying
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`degrees of success. For example, it is stated that in some
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`instances dehydrohalogenation was unsuccessful. In another
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`instance, a protracted reaction time (3 days) was required, or
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`relatively low product yield (40%, 65%) was obtained.
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`Tarrant, et al., J. Am. Chem. Soc., 77, 2783—2786 (1955)
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`described the synthesis of CF3CH—CF2 starting with: (1)
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`3-bromo-1,1,3,3-pentafluoropropane and reacting it with a
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`hot solution of KOH in water; and (2) 3-bromo-1,1,3,3-
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`tetrafluoropropene, reacting it with HF at 150 C and neu-
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`tralizing the reaction products with a KOH solution.
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`Kimura, et al., J. Org. Chem. 48, 195—198 (1983)
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`described multi-phase dehydrohalogenation of brominated
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`compounds using aqueous KOH and a phase transfer cata-
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`lyst based on polyethylene glycols and polyethylene glycol-
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`grafted copolymers. The preparation of fluoropropenes by
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`the dehydrohalogenation of fluoropropane using aqueous
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`KOH and a phase transfer catalyst, but with improved yields
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`and selectivity is disclosed by U.S. Pat. No. 6,548,719.
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`There is a continuing need for means by which fluoro-
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`propenes can be produced commercially with high yield and
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`selectivity, either catalytically or non-catalytically.
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`Page 2 of 8
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`Page 2 of 8
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`

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`US 7,230,146 B2
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`3
`Both methods dehydrohalogenate a halopropane having
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`the formula:
`
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`CF3C(YR1)C(XNHPR2)
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`wherein R1, R2, X and Y are independently hydrogen or a
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`halogen selected from fluorine, chlorine, bromine and
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`iodine, provided that at least one of R1, R2, X and Y is a
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`halogen and there is at least one hydrogen and one halogen
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`on adjacent carbon atoms.
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`Included among the halopropanes that can be included in
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`the present
`invention is 1,1,1,3,3-pentafluoropropane or
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`
`and
`HFC-245fa
`1-chloro-1,3,3,3-tetrafluoropropane
`or
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`HCFC-244fa. Various methods for producing these materi-
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`als are described in U.S. Pat. Nos. 5,710,352; 5,969,198;
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`5,728,904; and 6,023,004. Another method described in U.S.
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`Pat. No. 5,574,192 is said to be economical, amenable to
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`large-scale application and uses readily available raw mate-
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`rials. The process of that patent uses two steps as follows: (1)
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`formation of CCl3CH2CHCl2 by the reaction of CCl4 with
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`vinyl chloride; and (2) conversion of CCl3CH2CHCl2 to
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`CF3CH2CHF2 and CF3CH2CHFCl by reaction with HF in
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`the presence of a fluorination catalyst selected from anti-
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`mony halides, niobium halides, arsenic halides, tantalum
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`halides;
`tin halides;
`titanium halides; antimony mixed
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`halides; niobium mixed halides, arsenic mixed halides,
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`tantalum mixed halides, mixed tin halides; mixed titanium
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`halides and mixtures thereof. Under-fluorinated materials,
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`such as CF3CH2CHCl2, may be recycled in subsequent runs.
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`The under-fluorinated material CF3CH2CHClF, or HFC-
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`244fa, can also be used as a starting material in the present
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`invention for producing a fluoropropene. Thus, the above-
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`described process can be utilized to obtain two different
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`starting materials for the process of the present invention.
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`Furthermore, commercial quantities of CF3CH2CF2H are
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`available from Honeywell International, Inc., Morristown,
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`N.J., for use as the starting material of the present process for
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`direct conversion to the fluoroalkene CF3CH=CFH by
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`dehydrofluorination according to either process disclosed
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`herein. Other useful starting materials for the production of
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`fluoropropenes and/or fluorohalopropenes include the fol-
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`lowing: CF3CH2CF2Br; CF3CH2CF2l; CF3CHFCF2Br;
`
`
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`CF3CH2CH2l;
`CF3CH2CH2Cl;
`CF3CH2CH2Br;
`
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`CF3CH2CFHCl;
`CF3CHBrCF2Br;
`CF3CHClCF2C1;
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`CF3CH2CCl3;
`CF3CH2CFHBr;
`CF3CHClCF2H;
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`CF3CH2CF3; and the like.
`
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`
`In another embodiment of the invention, HCFC-244fa
`
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`and/or HFC-245fa can be prepared by fluorinating 1,1,1,3,
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`3-pentachloropropane(HCC-240fa). In this embodiment, in
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`a preliminary step, the process of the invention involves the
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`formation of HCFC-244fa and/or HFC-245fa by reacting
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`1,1,1,3,3-pentachloropropane (HCC-240fa) with hydrogen
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`in the vapor phase, or the liquid phase,
`fluoride (HF)
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`preferably in the presence of a fluorination catalyst as is well
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`known in the art.
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`The result is a reaction product of one or both of the two
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`products, HCFC-244fa and/or HFC-245fa. In the preferred
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`embodiment of the invention, the HF to HCC-240fa mole
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`ratio preferably ranges from about 2:1 to about 100:1; more
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`preferably from about 4:1 to about 50:1 and most preferably
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`from about 5:1 to about 20:1.
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`Useful fluorination catalysts include, but are not limited
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`to, transition metal halides, Group IVb and Vb metal halides,
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`and combinations thereof, preferably supported on activated
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`carbon or fluorinated alumina. More specifically, preferred
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`vapor phase fluorination catalysts non-exclusively include
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`SbCl5, SbCl3, SbF5, TaCl5, SnCl4, NbCl5, TiCl4, MoCl5,
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`10
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`15
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`20
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`25
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`30
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`35
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`40
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`45
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`50
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`55
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`60
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`65
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`Page 3 of 8
`
`4
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`Cr2O3, Cr2O3/A1203, Cr2O3/AlF3, Cr2O3/carbon, CoCl2/
`
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`Cr2O3/A1203, NiCl2/Cr2O3/A1203, CoCl2/AlF3, NiCl2/AlF3
`
`
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`
`and mixtures thereof. Preferred liquid phase fluorination
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`catalysts non-exclusively include SbCl5, SbCl3, SbF5,
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`TaCl5, SnCl4, NbCl5, TiCl4, and MoCl5. It is understood that
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`after pre-treatment with HF or during reaction in the pres-
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`ence of HF the above mentioned catalyst will be partially
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`fluorinated Chromium oxide/aluminum oxide catalysts are
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`
`described in U.S. Pat. No. 5,155,082 which is incorporated
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`herein by reference. Chromium (III) oxides such as crystal-
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`line chromium oxide or amorphous chromium oxide are
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`preferred vapor phase fluorination catalysts with amorphous
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`chromium oxide being the most preferred vapor phase
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`catalyst. Chromium oxide (Cr2O3) is a commercially avail-
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`able material which may be purchased in a variety of particle
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`sizes. Unsupported SbCl5 and SbCl3 halides are preferred
`
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`liquid phase catalysts. Both of these liquid phase catalysts
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`are commercially available and well known in the art.
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`Fluorination catalysts having a purity of at least 98% are
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`preferred. The fluorination catalyst is present in an amount
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`suflicient to drive the reaction. The fluorination reaction may
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`be conducted in any suitable fluorination reaction vessel or
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`reactor but it should preferably be constructed from mate-
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`rials which are resistant to the corrosive effects of hydrogen
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`fluoride such as nickel and its alloys, including Hastelloy,
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`Inconel, Incoloy, and Monel or vessels lined with fluo-
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`ropolymers.
`
`Any water in the hydrogen fluoride (HF) will react with
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`and deactivate the fluorination catalyst. Therefore substan-
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`tially anhydrous hydrogen fluoride is preferred. By “sub-
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`
`stantially anhydrous” it is meant that the HF contains less
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`than about 0.05 weight % water and preferably contains less
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`than about 0.02 weight % water. However, one of ordinary
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`skill in the art will appreciate that the presence of water in
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`the HF can be compensated for by increasing the amount of
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`catalyst used.
`
`
`The liquid phase fluorination of HCC-240fa is preferably
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`
`conducted at a temperature of from about 50° C. to about
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`and 450° C., more preferably from about 60° C. to about
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`180° C. and most preferably from about 65° C. and 150° C.
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`Fluorination is preferably conducted at a pressure of from
`
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`
`
`about 50 psig to about 400 psig. The reactor is preferably
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`
`
`preheated to the desired fluorination reaction temperature
`
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`while anhydrous HF is fed to the reactor. The HCC-240fa
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`
`and HF may be fed to the reactor at the desired temperatures
`
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`
`
`and pressures that are described herein.
`In a preferred
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`
`
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`
`
`
`embodiment of the invention, either or both of the HCC-
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`
`
`240fa and HF are pre-vaporized or preheated prior to enter-
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`ing the reactor.
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`
`When HCC-240fa and HF are reacted in a vapor phase
`
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`
`with the fluorination catalyst the HCC-240fa and HF may be
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`fed to the reactor at the desired temperatures and pressures
`
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`
`
`that are described herein. The reactor is preheated to the
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`fluorination reaction temperature while anhydrous HF is fed
`
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`to the reactor. The HCC-240fa and HF may be fed to the
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`reactor at any convenient temperature and pressure. In a
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`
`
`preferred embodiment either or both of the HCC-240fa and
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`
`HF are pre-vaporized or preheated to a temperature of from
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`about 30° C. to about 300° C. prior to entering the reactor.
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`In another embodiment, the HCC-240fa and HF are vapor-
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`ized in the reactor.
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`The HF and HCC-240fa feeds are then adjusted to the
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`
`
`desired mole ratio. The HF to HCC-240fa mole ratio pref-
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`
`erably ranges from about 2:1 to about 100:1; more prefer-
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`
`ably from about 4:1 to about 50:1 and most preferably from
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`about 5:1 to about 20:1.
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`Page 3 of 8
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`

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`
`
`US 7,230,146 B2
`
`
`
`
`
`
`
`
`
`5
`The fluorination reaction is conducted at a preferred
`
`
`
`
`
`
`
`
`temperature ranging from about 80° C. to about 400° C.;
`
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`
`
`more preferably from about 100° C. to about 350° C. and
`
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`
`
`most preferably from about 200° C. to about 330° C. Reactor
`
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`
`pressure is not critical and can be superatmospheric, atmo-
`
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`spheric or under vacuum. The vacuum pressure can be from
`
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`about 5 torr to about 760 torr. The reactant vapor is allowed
`
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`
`to contact the fluorination catalyst for from about 0.01 to
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`about 240 seconds, more preferably from about 0.1 to about
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`60 seconds and most preferably from about 0.5 to about 20
`
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`seconds.
`
`Usually the process flow of the HCC-240fa and HF is in
`
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`
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`the down direction through a bed of the catalyst. Before each
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`
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`use, the catalyst is preferably dried, pre-treated and acti-
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`
`
`
`vated. It may also be advantageous to periodically regener-
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`
`
`ate the catalyst after prolonged use while in place in the
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`
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`reactor.
`
`For Cr2O3, Cr2O3/A1203, Cr2O3/AlF3, Cr2O3/carbon,
`
`
`
`
`
`CoCl2/AlF3,
`CoCl2/Cr2O3/A1203, NiCl2/Cr2O3/A1203,
`
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`
`
`
`
`
`
`
`
`NiCl2/AlF3 catalysts, pre-treatment can be done by heating
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`the catalyst to about 250° C. to about 430° C. in a stream of
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`nitrogen or other inert gas. The catalyst may then be
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`activated by treating it with a stream of HF diluted with a
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`large excess of nitrogen gas in order to obtain high catalyst
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`activity. Regeneration of the catalyst may be accomplished
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`by any means known in the art such as, for example, by
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`passing air or air diluted with nitrogen over the catalyst at
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`temperatures of from about 100° C.
`to about 400° C.,
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`preferably from about 200° C. to about 375° C., for from
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`about 1 hour to about 3 days, depending on the size of the
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`reactor. For SbCl5, SbCl3, TaCl5, SnCl4, NbCl5, TlCl4,
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`MoCl5 catalysts, supported on an solid support such as
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`activated carbon, pre-treatment or activation can be done by
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`first heating the catalyst to about 30° C. to 250° C. in a
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`stream of nitrogen or other inert gas. It is then treated with
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`a stream of HF in the absence or presence of an oxidizing
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`agent such as chlorine gas in order to obtain high catalyst
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`activity. In addition, the catalyst may optionally be kept
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`active by co-feeding chlorine to the reactor during reaction.
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`HCFC-244fa and HFC-245fa may be recovered from the
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`fluorination reaction product mixture comprised of unre-
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`acted starting materials and by-products, including HCl, by
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`any means known in the art, such as by scrubbing, extrac-
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`tion, and preferably distillation. For example, the distillation
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`may be preferably conducted in a standard distillation col-
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`umn at a pressure, which is less than about 300 psig,
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`preferably less than about 150 psig and most preferably less
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`than 100 psig. The pressure of the distillation column
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`inherently determines the distillation operating temperature.
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`HCl may be recovered by operating the distillation column
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`at from about —40° C. to about 25° C., preferably from about
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`—40° C.
`to about —20° C. Single or multiple distillation
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`columns may be used. The distillate portion includes sub-
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`stantially all the HCFC-244fa, HFC-245fa, unreacted HF
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`and HCl produced in the reaction as well as any other
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`impurities. In the preferred embodiment, HCFC-244fa and
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`the HFC-245fa are separated from all other reaction by-
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`products and unreacted HF for further reaction in step (b)
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`described herein. In the preferred embodiment, any HF
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`present may also be recovered and recycled back for sub-
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`sequent fluorination reactions. 1234ze is formed by the
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`dehydrochlorination of 1-chloro-1,3,3,3-tetrafluoropropane
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`(HCFC-244fa) or the dehydrofluorination of 1,1,1,3,3-pen-
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`tafluoropropane (HFC-245fa).
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`According to one method of the present invention, the
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`halopropane is dehydrohalogenated with an alkali metal or
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`alkaline earth metal hydroxide in a non-aqueous, non-
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`6
`alcohol solvent for the alkali metal or alkaline earth metal
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`hydroxide that is at least partially miscible with the halo-
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`propane. Alkali metal and alkaline earth metal hydroxides
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`suitable for use in the present invention include, but are not
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`limited to LiOH, KOH, NaOH, CaO, Ca(OH)2, CaCO3,
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`the
`and/or lime stone, and the like. By either method,
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`dehydrochlorination of HCFC-244fa proceeds as follows:
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`The dehydrohalogenation is performed within a tempera-
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`ture range at which the halopropane will dehydrohalogenate.
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`According to one aspect of this method, alkali metal or
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`alkalin eearth metal hydroxide pellets are dissolved in the
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`solvent with agitation under otherwise ambient conditions.
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`The halopropane is then bubbled through the alkali metal or
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`alkaline earth metal hydroxide solution as the temperature of
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`the solution is gradually increased by heating. Gradual
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`heating is continued until initiation of dehydrohalogenation
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`is observed, after which the temperature at which dehydro-
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`halogenation initiation occurred is maintained until comple-
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`tion of the process.
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`In carrying out the process, the molar ratio of alkali metal
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`or alkaline earth metal hydroxide relative to the amount of
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`halopropane is from about 1:1 to about 20,1, preferably from
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`about 1:1 to about 15: 1; and more preferably from about 1:1
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`to about 12:1; for example, from 1:1 to about 10:1. In the
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`preferred embodiment of the invention, the caustic strength
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`of the caustic solution is from about 2 wt % to about 100 wt
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`%, more preferably from about 5 wt % to about 90 wt % and
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`most preferably from about 10 wt % to about 80 wt %. The
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`reaction is preferably conducted at a temperature of from
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`about 20° C. to about 150° C., more preferably from about
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`30° C. to about 110° C. and most preferably from about 40°
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`C. to about 90° C. The reaction pressure is not critical. The
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`reaction can be conducted at atmospheric pressure, super-
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`atmospheric pressure or under vacuum. The vacuum pres-
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`sure can be from about 5 torr to about 760 torr. Preferably,
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`the reaction is conducted at atmospheric or super-atmo-
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`spheric pressure.
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`The dehydrohalogenation reaction can be accomplished
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`using a solution of at least one alkali metal or alkaline earth
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`metal hydroxide in a non, aqueous, non-alcohol solvent for
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`the alkali metal or alkaline earth metal hydroxide that is
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`essentially miscible with the halopropane. For purposes of
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`the present invention, “essentially miscible” means that an
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`agitated mixture containing 50 wt. % halpropane and 50 wt.
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`% solvent does not separate to form more than one liquid
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`phase over the temperature range at which the dehydroha-
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`logenation will occur, or, if such separa