(12) Ulllted States Patent
`
`
`
`
`Van Der Puy et al.
`
`
`
`
`
`
`(10) Patent No.:
`
`
`(45) Date of Patent:
`
`
`
`
`
`US 7,560,602 B2
`
`
`
`Jul. 14, 2009
`
`US007560602B2
`
`
`
`1/1998 Tung ........................ .. 570/166
`5,710,352 A *
`
`
`
`
`
`4/1999 Swain et al.
`5,895,639 A *
`423/483
`
`
`
`
`
`8/1999 \Tappa et al.
`5,945,573 A *
`570/175
`
`
`
`
`
`
`
`
`
`
`
`2 :
`Y/Ia;1]_ier_Puy
`
`
`
`
`
`7/2000 \Ia lairiiim et ai 1
`6,093,859 A *
`
`
`
`
`
`2,2001 R3512”,
`' """"""" "
`6:194:619 B1
`5/2001 Sievert etal.
`............. .. 570/134
`6,229,058 B1*
`
`
`
`
`
`
`
`4/2002 \Tappa et al.
`.... ..
`6,369,284 B1*
`570/156
`
`
`
`
`
`
`5/2002 Yamada etal.
`............ .. 510/412
`6,395,700 B1*
`
`
`
`
`
`
`4/2003 \Taireta1.
`6,548,719 B1
`
`
`
`
`
`570/160
`3/2007 Vlukhopadhyay et al.
`7,189,884 B2*
`
`
`
`
`
`6/2007 Vlerkelet a1.
`............. .. 570/155
`7,230,146 B2*
`
`
`
`
`
`
`
`
`
`
`
`
`................. .. 570/175
`7,285,690 B2: 10/2007 Rao et al.
`10 2007 Rao eta.
`7,285,692 B2
`.... ..
`570 176
`
`
`
`
`
`
`
`==<
`2004/0236161 A1* 11/2004 Rao et al.
`.... ..
`570/177
`
`
`
`:33:/32:23:: :1. 1/222: $$§f$§:$1;;;;;'11',"::: 2:3/1::
`
`
`
`
`
`
`*
`.
`570/171
`2005/0245774 A1 * 11/2005 \/Iukhopadhyay et al.
`
`
`
`
`
`
`2006/0106263 A1
`5/2006 \/11lleret al.
`.............. .. 570/155
`
`
`
`
`
`
`
`FOREIGN PATE1\T DOCUMENTS
`
`
`
`WO98/33755
`8/1998
`
`570/175
`
`
`
`.... ..
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`WO
`
`
`
`
`
`OTHER PUBLICATIONS
`
`
`1ll'ly3.l'l S
`, C 3.
`0I1'1I1'l11I1lC3. l0Il
`63.0 l0IlS 0
`I
`11010
`6 HS
`
`
`
`.
`t.
`t.
`Kn
`C
`O1 fi
`1 “R
`t IL t
`fF1
`
`
`
`
`
`
`13, Catalytic Hydrogenation of Perfluoro Olefins”, Bulletin of the
`
`
`
`
`
`
`
`
`
`
`
`
`
`Academy of Sciences of teh USSR, Division of Chemical Sciences,
`1960, XP000578879a PP~ 1312-1317
`
`
`
`
`
`* Cited b examiner
`Y
`Primary Examiner—Jafar Parsa
`
`
`
`(74) Attorney, Agent, or Firm—Bruce 0. Bradford
`
`
`
`
`
`(54) PROCESS FOR MANUFACTURE OF
`
`
`
`
`FLUORINATED OLEFINS
`
`
`
`
`(75)
`
`
`
`
`
`
`Inventors: MichaelVan Der Puy,A1nherst,NY
`
`
`
`
`(US); Gemge R‘ C°°k’ Buffa1°’NY
`
`
`
`
`(US); Peter H. Scheidle, Wheatfield, NY
`(U323 K°‘_’“1 D-Uh“°h>,A,1den= NY
`
`
`
`(US);Ha1y01l WaI1gaW1111amSV}11esNY
`
`
`
`
`(US); Hsueh Sung Tung, Getzvllle, NY
`
`
`
`
`
`(US)
`
`
`
`
`
`
`( >x< ) Notice:
`
`
`
`
`
`
`(73) Assignee: Honeywell International Inc.’
`
`
`
`
`
`
`
`Morfistowna N] (US)
`.
`’.
`Subject to any disclaimer the term Ofthis
`
`
`
`
`
`
`
`es
`1;,;;,;;g,deg g;
`
`
`
`
`"
`VS"
`"
`"
`
`
`
`
`
`(21) Appl. NO‘: 11/588,464
`
`
`
`
`
`
`
`3’
`
`
`(22)
`
`
`
`Filed:
`
`
`Oct. 27, 2006
`
`
`
`
`
`
`(65)
`
`Prior Publication Data
`
`
`
`
`
`
`
`US 2007/0179324 A1
`Aug. 2, 2007
`.
`.
`
`
`
`
`
`
`Related U'S' Apphcatlon Data
`(60) Provisional application No. 60/763,086, filed on Jan.
`
`
`
`
`
`
`
`
`
`
`
`
`
`27, 2006, provisional application No. 60/733,355,
`filed on Nov. 3, 2005.
`
`
`
`
`(51)
`
`
`
`
`(56)
`
`Int CL
`
`
`(2006.01)
`C07C 17/00
`
`
`
`(2006.01)
`C07C 17/10
`
`
`
`(52) U.S. Cl.
`...................... .. 570/156; 570/155; 570/176
`
`
`
`
`
`
`
`
`
`
`(58) Field of Classification Search ............... .. 570/155,
`
`570/1 55, 175
`
`
`
`
`
`
`
`See appficatjon me for c0mp1ete Search history.
`_
`
`
`References Clted
`U.S. PATENT DOCUMENTS
`
`
`
`4,033,899 A *
`7/1977 Bennett et al.
`.............. .. 502/22
`
`
`
`
`
`
`4,138,355 A *
`2/1979 Ferstandig ........... .. 252/183.14
`
`
`
`
`
`5,180,860 A *
`1/1993 Fernandez et al.
`........ .. 570/157
`
`
`
`
`
`
`5,334,783 A *
`8/1994 Freudenreich et al.
`.... .. 570/153
`
`
`
`
`
`5,396,000 A
`3/1995 Nappa et al.
`
`
`
`
`5,672,787 A
`9/1997 Bielefeldt et al.
`
`
`
`5,679,875 A
`10/1997 Aoyama et al.
`
`
`
`
`
`(57)
`
`
`
`ABSTRACT
`
`
`
`
`
`
`
`
`
`Apropess for the productlon offluonnated olefins, preferably
`
`
`
`
`
`
`fluorinated propenes, by contact1ng.a feed stream contaimng
`
`
`
`
`
`
`
`
`
`a fluorinated olefin and hydrogen with a first amount of cata-
`
`
`
`
`
`
`
`
`lyst to produce the hydrofluorocarbon, wherein a first exit
`
`
`
`
`
`
`
`stream contains unreacted fluorinated olefin and hydrogen;
`contacting the first exit stream with a second amount of cata-
`
`
`
`
`
`
`
`
`
`lyst to produce a hydrofluorocarbon, wherein the second
`
`
`
`
`
`
`
`amount of catalyst is preferably greater than the first amount
`
`
`
`
`
`
`
`
`of catalyst; and contacting the hydrofluorocarbon with a cata-
`
`
`
`
`
`
`
`
`lyst for dehydrohalogenation to produce a product stream of
`
`
`
`
`
`
`fluorinated olefin.
`
`
`
`
`13 Claims, 1 Drawing Sheet
`
`
`
`
`
`
`
`
`
`
`
`
`
`Page 1 of 11
`
`Arkema Exhibit 1033
`
`Arkema Exhibit 1033
`
`Page 1 of 11
`
`

`
`
`
`U.S. Patent
`
`
`
`Jul. 14, 2009
`
`
`
`
`
`US 7,560,602 B2
`
`
`
`
`
`
`
`
`
`
`
`HMMDQE
`
`
`
`
`
`NNMDOE
`
`newUom8.
`
`
`
`
`H.....1§...m«“«mafia»,
`
`
`.»»»»>..o.o»»»9.o..o._vo»o.o.+.o».II
`
`
`
`
`
`
`
`-oxn.Emo
`
`
`
`
`zoF<zmwo,.w..mzonbmnmm
`
`
`
`Page 2 of 11
`
`Page 2 of 11
`
`
`

`
`
`
`US 7,560,602 B2
`
`1
`
`PROCESS FOR MANUFACTURE OF
`
`
`
`FLUORINATED OLEFINS
`
`
`
`CROSS-REFERENCES TO RELATED
`
`
`APPLICATIONS
`
`
`2
`
`
`olefins of the present invention comprise one or more C2 to
`
`
`
`
`
`
`C6 fluoroalkenes, preferably compounds having a formula as
`
`
`
`
`
`
`follows:
`
`x1cFz1c—z
`
`This application is related to and claims the priority benefit
`
`
`
`
`
`
`
`
`of provisional application 60/733,355, filed on Nov. 3, 2005,
`
`
`
`
`
`
`
`which is incorporated herein by reference.
`
`
`
`
`This application is also related to and claims the priority
`
`
`
`
`
`
`
`
`benefit of provisional application 60/763,086 filed on Jan. 7,
`
`
`
`
`
`
`2006, which is incorporated herein by reference.
`
`
`
`
`
`Also incorporated herein by reference are of the following
`
`
`
`
`
`
`U.S. Applications which are filed concurrently herewith and
`
`
`
`
`
`
`
`identified by U.S. patent application Ser. Nos. 1 1/588,465 and
`
`
`
`
`
`
`
`
`1 1/5 88,67 1 .
`
`
`
`
`10
`
`15
`
`BACKGROUND OF THE INVENTION
`
`
`
`
`Fluorinated olefins, as a class, have many and varied uses,
`
`
`
`
`
`
`
`
`including as chemical intermediates and monomers.
`
`
`
`
`
`Several methods for preparing fluorinated olefins are
`
`
`
`
`
`
`
`known. For example, U.S. Pat. No. 5,679,875 discloses meth-
`
`
`
`
`
`
`
`
`
`ods for manufacturing 1,1,1,2,3-pentafluoropropene and 1,1,
`
`
`
`
`
`
`1,2,3-pentafluoropropane; U.S. Pat. No. 6,031,141 discloses
`
`
`
`
`
`
`a catalytic process using chromium-containing catalysts for
`
`
`
`
`
`
`
`the dehydrofluorination of hydrofluorocarbons to fluoroole-
`
`
`
`
`fins; U.S. Pat. No. 5,396,000 discloses a process for produc-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`ing CF3CHFCH2F using vapor phase catalytic dehydrohalo-
`genation to produce CF3CF:CHF and HF, followed by vapor
`
`
`
`
`
`
`phase catalytic hydrogenation of CF3CF:CHF in the pres-
`
`
`
`
`
`
`ence of HF; U.S. Pat. No. 6,548,719 discloses a process for
`
`
`
`
`
`
`
`
`
`producing fluoroolefins by dehydrohalogenating a hydrof-
`
`
`
`
`luorocarbon in the presence of a phase transfer catalyst; U.S.
`
`
`
`
`
`
`
`Publication No. 2006/0106263 discloses the production and
`
`
`
`
`
`
`
`
`purification of hydrofluoroolefin compounds; and WO98/
`
`
`
`
`
`
`33755 discloses catalytic process for the dehydrofluorination
`
`
`
`
`
`
`
`of hexafluoropropanes to pentafluoropropenes.
`
`
`
`Applicants have discovered that the processes of the type
`
`
`
`
`
`
`
`
`described above have disadvantages and/or are not as effec-
`
`
`
`
`
`
`
`
`tive and/or economical as would be practically necessary for
`
`
`
`
`
`
`
`large scale commercial production. For example, applicants
`
`
`
`
`
`
`
`have come to appreciate that it is generally not possible, by
`
`
`
`
`
`
`
`
`following the teachings of the above publications alone, to
`
`
`
`
`
`
`
`achieve a process having at once a high degree of ultimate
`
`
`
`
`
`
`
`conversion and a high degree of selectivity to the desired
`
`
`
`
`
`
`
`
`fluorinated olefin.
`
`
`
`SUMMARY OF THE INVENTION
`
`
`
`
`Applicants have come to appreciate in one respect of the
`
`
`
`
`
`
`
`invention, that none of the above-noted publications disclose
`
`
`
`
`
`
`an integrated process comprising the steps of selectively
`
`
`
`
`
`
`
`
`hydrogenating one or more highly fluorinated olefins to pro-
`
`
`
`
`
`
`
`duce one or more hydrofluorocarbons, followed by the step of
`
`
`
`
`
`
`dehydrofluorinating the resultant hydrofluorocarbons(s) to
`
`
`
`
`produce one or more desired fluorinated olefins, particularly
`
`
`
`
`
`
`
`propene, and HF, nor do they disclose such a process com-
`
`
`
`
`
`
`
`
`
`bined with a highly effective HF recovery step.
`
`
`
`
`
`
`Applicants have developed, in one aspect of the present
`
`
`
`
`
`
`
`invention, processes for the synthesis of fluorinated alkenes,
`
`
`
`
`
`
`
`and preferable fluorinated olefins having from three to six
`
`
`
`
`
`
`
`
`carbon atoms and a degree of fluorine substitution of N. In
`
`
`
`
`
`
`certain highly preferred embodiments, the desired fluorinated
`
`
`
`
`
`
`
`
`20
`
`
`
`25
`
`
`30
`
`
`
`35
`
`
`40
`
`
`
`45
`
`50
`
`
`
`55
`
`
`60
`
`
`
`65
`
`
`Page 3 of 11
`
`where X1 is a C1, C2, C3, C4, or C5 unsaturated, substituted
`
`
`
`
`
`
`
`or unsubstituted, alkyl radical, each R is independently Cl, F,
`
`
`
`
`
`
`
`Br, I or H, and z is 1 to 3. Highly preferred among such
`
`
`
`
`
`
`
`
`
`compounds are propenes and butenes having from 3 to 5
`
`
`
`
`
`
`
`fluorine substituents, and among these tetrafluoropropenes
`
`
`
`
`
`
`(HFO-1234) are especially preferred.
`
`
`
`invention comprise
`Preferred processes of the present
`
`
`
`
`
`
`
`reacting a fluorinated olefin starting material with a degree of
`
`
`
`
`
`
`
`halogen substitution of N+1 having substantially the same
`
`
`
`
`
`
`
`number of carbon atoms as the fluorinated olefin(s) to be
`
`
`
`
`
`
`
`synthesized with a degree of halogen substitution of N. Pref-
`
`
`
`
`
`
`erably the fluorinated olefin starting material having a degree
`
`
`
`
`
`
`
`
`of fluorine substitution of N+1 is exposed to reaction condi-
`
`
`
`
`
`
`
`tions effective to produce a reaction product containing one or
`
`
`
`
`
`
`
`more fluorinated alkanes having the same number of carbons
`
`
`
`
`
`
`
`
`atoms as the olefin. In one preferred aspect of the present
`
`
`
`
`
`
`
`
`
`invention, this olefin conversion step comprises a reaction
`
`
`
`
`
`
`
`that is sometimes referred to herein for convenience, but not
`
`
`
`
`
`
`
`
`necessarily by way of limitation, as a reduction or hydroge-
`
`
`
`
`
`nation step. The fluorinated alkane is then preferably con-
`
`
`
`
`
`
`
`
`verted to a fluorinated olefin having a degree of fluorine
`
`
`
`
`
`
`
`substitution ofN. In one preferred aspect ofthe present inven-
`
`
`
`
`
`
`tion, this alkane conversion step comprises a reaction that is
`
`
`
`
`
`
`
`
`sometimes referred to herein for convenience, but not neces-
`
`
`
`
`
`
`
`
`sarily by way oflimitation, as a dehydrohalogenation reaction
`
`
`
`
`
`or more particularly in certain embodiments as a dehydroflu-
`
`
`
`
`
`
`orination or dehydrochlorination reaction.
`
`
`
`According to one aspect of the present invention, the
`
`
`
`
`
`
`
`present processes preferably comprise the steps of
`
`
`
`
`
`
`(a) hydrogenating, preferably in a multistage reaction, a com-
`
`
`
`
`
`
`pound of formula (I)
`
`
`(CXnY3—n)(CRla R2b)ZCX:CHmX2—m
`
`(1)
`
`
`
`under conditions effective to form at least one fluorinated
`
`
`
`
`
`
`alkane of formula (II)
`
`
`
`(CXnY3—n)(CRlaR2b)ZCHXCHm+lX2—m
`
`(H)
`
`
`
`where:
`
`
`
`
`each X is independently Cl, F, I or Br;
`
`
`
`
`
`eachY is independently H, Cl, F, I or Br;
`
`
`
`
`
`each R1 is independently H, Cl, F, I, Br or unsubstitued or
`
`
`
`
`
`halogen substituted methyl or ethyl radical;
`
`
`
`
`
`each R2 is independently H, Cl, F, I, Br or unsubstitued or
`
`
`
`
`
`halogen substituted methyl or ethyl radical;
`
`
`
`
`
`n is 1, 2 or 3;
`
`
`a and b are each 1 or 2, provided that a+b:2;
`
`
`
`
`
`
`
`m is 0, 1 or2; and
`
`
`
`
`Z is 0,1,2 or 3, and
`
`
`
`(b) deydrohalogenating the compound of formula (II) under
`
`
`
`
`
`
`
`conditions effective to produce a fluoroolefin with a lower
`
`
`
`
`
`
`degree of fluorine substitution than the compound of formula
`
`
`
`
`
`
`
`(I), preferably to produce a compound of formula (III):
`
`
`
`
`
`
`(CXnY3—n)(CRlaR2b)ZCX:CHmX2—m
`
`
`
`(H1)
`
`
`
`where each n is the same value as in formula (I) and m is 0 or
`
`
`
`
`
`
`
`1.
`
`
`Page 3 of 11
`
`

`
`
`
`US 7,560,602 B2
`
`3
`
`In certain preferred embodiments, the reactant of formula
`
`
`
`
`
`
`
`(I) comprises a three carbon olefin of formula (IA) wherein z
`
`
`
`
`
`
`
`
`is 0, namely
`
`
`
`CX,,Y3_,,CX:CHmX2_m
`
`(IA)
`
`
`preferably at least about 80%, and more preferably at least
`
`
`
`
`
`
`
`about 90%, and even more preferably about 98%.
`
`
`
`
`
`
`
`
`
`4
`
`
`
`BRIEF DESCRIPTION OF THE DRAWING
`
`
`
`
`
`
`to produce a three carbon alkane of formula (IIA) as follows:
`
`
`
`
`
`
`
`(CX,,Y3_,,)CHXCHm+1X2—m
`
`
`
`(IIA)
`
`
`where X, Y, n, and m are all as indicated above, which com-
`
`
`
`
`
`
`
`
`pound is then dehydrohalogenated to form a compound of
`
`
`
`
`
`formula (IIIA)
`
`
`(CX,,Y3_,,)CX:CHmX2_m
`
`(IIIA)
`
`where n is the same value as in formula (IA) and m is 0 or 1.
`
`
`
`
`
`
`
`In certain highly preferred aspects of such embodiments, a
`
`
`
`
`
`
`
`saturated terminal carbon ofthe compounds of formulas (I) or
`
`
`
`
`
`(IA) is fully substituted with fluorine (for example, 11 on the
`
`
`
`
`
`
`
`saturated terminal carbon is 3 and each X on that carbon is F),
`
`
`
`
`
`
`
`
`and even more preferably 11 is 3 and each X in the compound
`
`
`
`
`
`
`
`
`is F.
`
`
`For three carbon embodiments of such preferred aspects,
`
`
`
`
`
`
`
`the compound of Formula (IA) is preferably a fluoropropene
`
`
`
`
`
`
`having from three to six fluorine substituents, and potentially
`
`
`
`
`
`
`
`
`other halogen substituents, including for example hexafluo-
`
`
`
`
`
`
`
`ropropene (that is, Z is 0, n is 3, m is 0, and all X are F) or
`
`
`
`
`
`
`
`pentafluoropropene (that is, Z is 0, n:3, m is 1, and all X are
`
`
`
`
`
`
`
`F), and the compound of formula (IIA) preferably comprises,
`
`
`
`
`
`
`
`and more preferably is selected from the group consisting of,
`
`
`
`
`
`
`
`
`one or more of the following fluorinated alkanes: chlorotrif-
`
`
`
`
`
`
`
`luoropropane (HCFC-244) and pentafluoropropane (HFC-
`
`
`
`
`
`245), and hexafluoropropane (HFC-236), including all iso-
`
`
`
`
`
`
`
`mers of each of these, but preferably 1-chloro, 1,3,3,3-
`
`
`
`
`
`
`
`
`
`tetrafluoropropane
`(HCFC-244fa),
`1,1,1,3,3-
`
`
`
`pentafluoropropane
`1,1,1,2,3-
`(HFC-245fa),
`
`
`
`pentafluoropropane
`(HFC-245eb),and
`1,1,1,2,3,3-
`
`
`
`(HFC-236ea).
`In certain preferred
`hexafluoropropane
`
`
`
`
`
`embodiments the fluorinated alkane produced by the conver-
`
`
`
`
`
`
`sion step has a degree of fluorine substitution of N+1.
`
`
`
`
`
`
`
`In preferred embodiments, the converting step (a) wherein
`
`
`
`
`
`
`
`
`the olefin is converted to an alkane is carried out under con-
`
`
`
`
`
`
`
`
`ditions effective to provide a formula (I) conversion ofat least
`
`
`
`
`
`
`about 40%, more preferably at least about 55%, and even
`
`
`
`
`
`
`
`
`
`more preferably at least about 70%. In certain preferred
`
`
`
`
`
`
`
`embodiments the conversion is at least about 90%, and more
`
`
`
`
`
`
`
`
`
`preferably about 99%. Further in certain preferred embodi-
`
`
`
`
`
`
`
`ments, the conversion of the compound of formula (I) to
`
`
`
`
`
`
`
`
`
`produce a compound of formula (II) is conducted under con-
`
`
`
`
`
`
`
`ditions effective to provide a formula (II) selectivity of at least
`
`
`
`
`
`
`
`about 60%, more preferably at least about 80%, and more
`
`
`
`
`
`
`
`
`
`preferably at least about 90%, and even more preferably about
`
`
`
`
`
`
`
`
`
`100%.
`
`In preferred embodiments, the converting step (b) wherein
`
`
`
`
`
`
`
`
`the alkane is converted to a fluorinated olefin having a degree
`
`
`
`
`
`
`
`offluorination ofN is carried out under conditions effective to
`
`
`
`
`
`
`
`provide a formula (II) conversion of at least about 40%, more
`
`
`
`
`
`
`
`
`preferably at least about 55%, and even more preferably at
`
`
`
`
`
`
`
`
`least about 70%. In certain preferred embodiments the con-
`
`
`
`
`
`
`
`
`version is at least about 90%, and more preferably about 95%.
`
`
`
`
`
`
`
`
`
`Further in certain preferred embodiments, the conversion of
`
`
`
`
`
`
`the compound of formula (II) to produce a compound of
`
`
`
`
`
`
`
`formula (III) is conducted under conditions effective to pro-
`
`
`
`
`
`
`
`vide a formula (III) selectivity of at least about 60%, more
`
`
`
`
`
`
`
`
`
`FIG. 1 is a schematic process flow diagram according to
`
`
`
`
`
`
`one embodiment of the present invention.
`
`
`
`
`
`FIG. 2 is a semi-schematic process flow diagram according
`
`
`
`
`
`
`to one embodiment of the hydrogenation step of the present
`
`
`
`
`
`
`
`
`invention.
`
`
`DETAILED DESCRIPTION
`
`
`
`
`One embodiment of the present invention will now be
`
`
`
`
`
`
`
`described in connection with FIG. 1 in which a feed stream 1
`
`
`
`
`
`
`
`comprising at least one fluorinated olefin having a degree of
`
`
`
`
`
`
`
`halogen substitution, and preferably a degree of fluorine sub-
`
`
`
`
`
`
`
`stitution, ofN+1 is subjected to a first converting step 50. The
`
`
`
`
`
`
`
`
`converting step 50 preferably involves also a feed stream 2
`
`
`
`
`
`
`
`
`comprising a reducing agent. The converting step 50 prefer-
`
`
`
`
`
`
`
`ably includes providing one or more reaction vessels, at least
`
`
`
`
`
`
`
`
`one of which preferably contains a reduction or hydrogena-
`
`
`
`
`
`
`tion catalyst, and introducing streams 1 and 2 into the
`
`
`
`
`
`
`
`
`vessel(s) under conditions effective to achieve the desired
`
`
`
`
`
`
`
`
`conversion.
`
`Although the streams 1 and 2 in the figure are shown for
`
`
`
`
`
`
`
`
`convenience as being separate streams, this is done for con-
`
`
`
`
`
`
`
`
`venience and the present invention is not so limited. For
`
`
`
`
`
`
`
`
`
`example, the streams could in certain embodiments be com-
`
`
`
`
`
`
`
`bined outside the vessel and then introduced to the vessel
`
`
`
`
`
`
`
`
`
`together, or in other embodiments stream 1 and stream 2
`
`
`
`
`
`
`
`might each comprise several separate streams, each of which
`
`
`
`
`
`
`
`
`is introduced into the vessel(s) at different times and/or at
`
`
`
`
`
`
`
`
`different locations. This same convention has been used and
`
`
`
`
`
`
`
`
`
`applies herein throughout to all use ofthe term “stream,” both
`
`
`
`
`
`
`
`
`in the description and in the figures, unless specifically indi-
`
`
`
`
`
`
`
`
`
`cated otherwise.
`
`
`The preferred converting step 50 produces at least one
`
`
`
`
`
`
`
`
`reaction product stream 3 which contains a fluorinated alkane
`
`
`
`
`
`
`
`in accordance with the present invention. Stream 3 is used as
`
`
`
`
`
`
`
`
`a reactant in conversion step 51, optionally stream 3 is further
`
`
`
`
`
`
`
`
`purified before fed to step 51, wherein the fluorinated alkane
`
`
`
`
`
`
`
`
`
`in stream 3 is converted to a fluorinated olefin have a degree
`
`
`
`
`
`
`
`ofhalogen substitution, and in certain preferred embodiments
`
`
`
`
`
`
`
`fluorine substitution, of N in accordance with the present
`
`
`
`
`
`
`
`invention. The converting step 51 preferably includes provid-
`
`
`
`
`
`
`
`ing one or more reaction vessels, at least one of which pref-
`
`
`
`
`
`
`
`
`
`erably contains a dehydrohalogenation catalyst and introduc-
`
`
`
`
`
`
`ing at least stream 3 into the vessel(s) under conditions
`
`
`
`
`
`
`
`
`effective to produce the desired fluoroolefin.
`
`
`
`
`
`In preferred embodiments, the conversion step 51 produces
`
`
`
`
`
`
`
`a reaction product which includes not only the desired fluo-
`
`
`
`
`
`
`
`
`
`
`roolefin, but also HF. In such embodiments it is generally
`
`
`
`
`
`
`
`
`preferred to introduce the stream 4 into a separation step 52 in
`
`
`
`
`
`
`
`which at least a portion ofthe HF is separated from the stream
`
`
`
`
`
`
`to produce at least a first stream 6 relatively rich (in compari-
`
`
`
`
`
`
`
`
`
`son to the feed stream 4) in the fluorinated olefin and at least
`
`
`
`
`
`
`
`
`
`a second stream relatively rich (in comparison to the feed
`
`
`
`
`
`
`
`
`
`stream 4) in HF.
`
`
`Preferred aspects of each of the steps 50, 51 and 52 are
`
`
`
`
`
`
`
`
`described below.
`
`
`
`
`
`The Reduction Step
`
`
`
`Although it is contemplated that the reduction step may be
`
`
`
`
`
`
`
`conducted in batch operation, it is preferred that the reduction
`
`
`
`
`
`
`
`reaction is carried out as a substantially continuous operation.
`
`
`
`
`
`
`Furthermore, while it is possible that the reduction reaction
`
`
`
`
`
`
`
`
`
`10
`
`15
`
`20
`
`
`
`25
`
`
`30
`
`
`
`35
`
`
`40
`
`45
`
`
`50
`
`
`
`55
`
`
`60
`
`
`
`65
`
`
`Page 4 of 11
`
`Page 4 of 11
`
`

`
`
`
`US 7,560,602 B2
`
`5
`
`may involve in certain embodiments a liquid phase reaction,
`
`
`
`
`
`
`
`it is contemplated that in preferred embodiments the reduc-
`
`
`
`
`
`
`
`
`tion reaction comprises, and even more preferably consists of,
`
`
`
`
`
`
`
`
`
`at least two vapor phase reaction stages.
`
`
`
`
`
`
`
`With respect to the number of reaction stages, applicants
`
`
`
`
`
`
`
`have found surprisingly and unexpectedly found that overall
`
`
`
`
`
`
`
`
`reaction conversion and selectivity can be achieved at rela-
`
`
`
`
`
`
`
`tively high levels by the use of at least two reaction stages
`
`
`
`
`
`
`
`
`
`
`wherein the first stage of reaction is conducted under condi-
`
`
`
`
`
`
`
`
`tions effective to achieve a first, relatively low rate of conver-
`
`
`
`
`
`
`
`
`sion to produce a first stage reaction effluent, and at least a
`
`
`
`
`
`
`
`
`second stage of reaction which is fed by at least a portion of
`
`
`
`
`
`
`
`said first stage effluent and which is conducted under condi-
`
`
`
`
`
`
`
`
`
`tions effective to achieve a second rate of conversion higher
`
`
`
`
`
`
`
`than said first rate. Preferably, reaction conditions are con-
`
`
`
`
`
`
`
`
`
`trolled in each ofthe first and second stages in order to achieve
`
`
`
`
`
`
`
`
`the desired conversion in accordance with the present inven-
`
`
`
`
`
`
`
`
`tion. As used herein,
`the term “reaction conditions” is
`
`
`
`
`
`
`
`
`intended to include the singular and means control of any one
`
`
`
`
`
`
`
`
`
`or more processing parameters which can be modified by the
`
`
`
`
`
`
`
`operator of the reaction to produce the conversion of the feed
`
`
`
`
`
`
`
`
`material in accordance with the teachings contained herein.
`
`
`
`
`
`
`
`By way of example, but not by way of limitation, conversion
`
`
`
`
`
`
`
`
`of the feed material may be controlled or regulated by con-
`
`
`
`
`
`
`
`
`trolling or regulating any one or more of the following: the
`
`
`
`
`
`
`
`
`temperature of the reaction, the flow rate of the reactants, the
`
`
`
`
`
`
`
`presence of diluent, the amount of catalyst present in the
`
`
`
`
`
`
`
`
`reaction vessel, the shape and size of the reaction vessel, the
`
`
`
`
`
`
`
`
`
`
`pressure of the reaction, and any one combinations of these
`
`
`
`
`
`
`
`
`and other process parameters which will be available and
`
`
`
`
`
`
`
`
`
`known to those skilled in the art in view of the disclosure
`
`
`
`
`
`
`
`
`
`contained herein.
`
`
`Applicants have found that in preferred embodiments the
`
`
`
`
`
`
`
`step of controlling the conversion in the first stage of the
`
`
`
`
`
`
`
`
`
`
`hydrogenation reaction is achieved by judicious selection and
`
`
`
`
`
`
`control of the amount of catalyst present in the first stage of
`
`
`
`
`
`
`
`reaction relative to the feed rate ofone or more ofthe reactants
`
`
`
`
`
`
`
`
`and/or by judicious selection and control of the reaction tem-
`
`
`
`
`
`
`
`perature, and preferably by judicious selection and control of
`
`
`
`
`
`
`
`both of these process parameters. The step of judiciously
`
`
`
`
`
`
`
`
`selecting the amount of catalyst to be used in the first stage of
`
`
`
`
`
`
`
`
`reaction includes the step of estimating the amount of catalyst
`
`
`
`
`
`
`
`
`theoretically needed to convert 100% of the feed material.
`
`
`
`
`
`
`
`Such an estimate can be obtained by any and all known
`
`
`
`
`
`
`
`
`
`methods for making such an estimate, which should be appar-
`
`
`
`
`
`
`
`ent to those skilled in the art in view of the teachings con-
`
`
`
`
`
`
`
`
`
`
`tained herein. In addition, the step ofjudiciously selecting the
`
`
`
`
`
`
`
`
`amount of catalyst may also involve conducting bench, pilot
`
`
`
`
`
`
`
`
`or similar studies to determine the amount of the particular
`
`
`
`
`
`
`
`
`catalyst being used which is needed to convert 100% of the
`
`
`
`
`
`
`
`
`feed material under the feed rate in other process parameters
`
`
`
`
`
`
`
`
`
`which have otherwise been chosen. Based upon this estimate,
`
`
`
`
`
`
`
`
`
`the preferred embodiments of the present invention then
`
`
`
`
`
`
`
`include the step of providing in the first stage of reaction an
`
`
`
`
`
`
`
`
`amount of catalyst that is substantially below the amount
`
`
`
`
`
`
`
`required for 100% conversion, and even more preferably is
`
`
`
`
`
`
`
`
`sufficiently low so as to result in a conversion of the feed
`
`
`
`
`
`
`
`
`
`olefin of from about 10% to about 60%, more preferably from
`
`
`
`
`
`
`
`
`
`about 10% to about 40%, and even more preferably from
`
`
`
`
`
`
`
`
`
`about 10% to 25%. Once again, those skilled in the art will
`
`
`
`
`
`
`
`
`
`
`appreciate that the step ofjudiciously choosing the amount of
`
`
`
`
`
`
`
`
`catalyst may further include running additional bench, pilot
`
`
`
`
`
`
`
`
`or other studies with the reduced amount of catalyst and
`
`
`
`
`
`
`
`
`
`adjusting the amount of catalyst accordingly. It is contem-
`
`
`
`
`
`
`
`plated that all such studies and estimates can be achieved
`
`
`
`
`
`
`
`
`
`without undue experimentation in view of the teachings con-
`
`
`
`
`
`
`
`tained herein.
`
`
`
`10
`
`15
`
`20
`
`
`
`25
`
`
`30
`
`
`
`35
`
`
`40
`
`
`
`45
`
`
`50
`
`
`
`55
`
`
`60
`
`
`
`65
`
`
`6
`
`In preferred embodiments, therefore, the step of control-
`
`
`
`
`
`
`
`ling conversion in the first reactor stage comprises feeding the
`
`
`
`
`
`
`
`
`
`olefin reactant into the first stage of reaction at a rate that is
`
`
`
`
`
`
`
`
`
`substantially above, and at least 60% about 90% above the
`
`
`
`
`
`
`
`
`
`productivity of the catalyst present in the first stage of reac-
`
`
`
`
`
`
`
`tion. Applicants have found, without being bound by or to any
`
`
`
`
`
`
`
`
`particular theory, that the use of such an excess of reactant in
`
`
`
`
`
`
`
`
`the first stage of reaction allows the feed materials to serve as
`
`
`
`
`
`
`
`
`
`a heat removal medium. Since the reduction or hydrogenation
`
`
`
`
`
`
`
`
`reaction of the present invention is generally exothermic, and
`
`
`
`
`
`
`usually substantially exothermic, the use of such excess feed
`
`
`
`
`
`
`
`
`material has the effect in preferred embodiments ofmaintain-
`
`
`
`
`
`
`
`ing the reactor temperature below that which would exist if an
`
`
`
`
`
`
`
`
`
`excess of feed material were not used, assuming all other
`
`
`
`
`
`
`
`
`
`process conditions were maintained the same.
`
`
`
`
`
`
`Applicants have found that the step of maintaining a very
`
`
`
`
`
`
`
`
`low conversion of reactant in accordance with the present
`
`
`
`
`
`
`
`invention in a first stage of reaction has an advantageous
`
`
`
`
`
`
`
`
`affect on the selectivity of the reaction to the desired alkane.
`
`
`
`
`
`
`
`In other words, although the amount of conversion which
`
`
`
`
`
`
`
`
`occurs in the first stage of reaction is controlled to be well
`
`
`
`
`
`
`
`
`below that which is desired for the overall reduction step,
`
`
`
`
`
`
`
`
`
`applicants have found that an improved, higher percentage of
`
`
`
`
`
`
`
`the feed material is converted to the desired alkane in the first
`
`
`
`
`
`
`
`
`
`reaction stage (that is, improved selectivity is achieved) by
`
`
`
`
`
`
`
`controlling the conversion as described herein. More specifi-
`
`
`
`
`
`
`
`cally, is preferred in many embodiments that the selectivity to
`
`
`
`
`
`
`
`the desired alkane in the first reaction stage is at least about
`
`
`
`
`
`
`
`
`
`
`80%, more preferably at least about 90%, and even more
`
`
`
`
`
`
`
`
`
`preferably at least about 95%, and in many preferred embodi-
`
`
`
`
`
`
`
`
`ments about 97% or greater.
`
`
`
`
`In certain preferred embodiments the step of controlling
`
`
`
`
`
`
`
`
`the conversion in the first reaction stage further includes
`
`
`
`
`
`
`
`
`removing heat from the reaction by cooling at least a portion
`
`
`
`
`
`
`
`ofthe reaction mixture. It is contemplated that those skilled in
`
`
`
`
`
`
`
`the art will be able to devise without undue experimentation
`
`
`
`
`
`
`
`
`and many means and mechanisms for attaining such cooling
`
`
`
`
`
`
`
`
`
`in view of the teachings contained herein and all such means
`
`
`
`
`
`
`
`
`
`and mechanisms are with the scope of the present invention.
`
`
`
`
`
`
`
`In preferred embodiments, at least a portion of the effluent
`
`
`
`
`
`
`from the first reaction stage is fed directly, or optionally after
`
`
`
`
`
`
`
`
`some further processing, to a second reaction stage in which
`
`
`
`
`
`
`
`the unreacted fluorinated olefin remaining in the effluent after
`
`
`
`
`
`
`
`
`the first reaction stage is converted to the fluorinated alkane in
`
`
`
`
`
`
`
`
`accordance with the present invention. More specifically is
`
`
`
`
`
`
`
`preferred that the second reaction stage or subsequent reac-
`
`
`
`
`
`
`
`
`tion stages ifpresent, is operated under conditions effective to
`
`
`
`
`
`
`
`convert the fluorinated olefin contained in the feed stream to
`
`
`
`
`
`
`
`
`the second reactor stage at a conversion rate that is greater
`
`
`
`
`
`
`
`
`than, and preferably substantially greater than, the conversion
`
`
`
`
`
`
`
`
`percentage in the first reaction stage. In certain preferred
`
`
`
`
`
`
`
`
`embodiments, for example, the conversion percentage in the
`
`
`
`
`
`
`
`second reaction stage is from about 20% to about 99%,
`
`
`
`
`
`
`
`
`depending in large part upon the total number of reactant
`
`
`
`
`
`
`
`
`stages used to affect the overall conversion step. For example,
`
`
`
`
`
`
`
`
`
`in embodiments consisting of a two-stage reaction system, it
`
`
`
`
`
`
`is contemplated that the conversion in the second reaction
`
`
`
`
`
`
`
`
`stage is preferably greater than 95%, and even more prefer-
`
`
`
`
`
`
`
`
`
`ably about 100%. However, as those skilled in the art will
`
`
`
`
`
`
`
`
`
`appreciate from the teachings contained herein, such a two-
`
`
`
`
`
`
`
`
`stage reaction may not be sufficient to produce the desired
`
`
`
`
`
`
`
`selectivity to the fluorinated alkane. In such cases, it is within
`
`
`
`
`
`
`
`the scope of the present invention that the conversion step
`
`
`
`
`
`
`
`
`
`may comprise greater than two reaction stages, including in
`
`
`
`
`
`
`
`
`some embodiments as many 10 or more reaction stages.
`
`
`
`
`
`
`In preferred embodiments, the fluorinated olefin conver-
`
`
`
`
`
`
`
`sion step of the present invention comprises about four reac-
`
`
`
`
`
`
`
`
`
`Page 5 of 11
`
`Page 5 of 11
`
`

`
`
`
`US 7,560,602 B2
`
`7
`
`is understood that the particular
`tion stages. Although it
`
`
`
`
`
`
`
`
`parameters used in each reaction stage may vary widely
`
`
`
`
`
`
`
`
`within the scope of the present invention, depending upon
`
`
`
`
`
`
`
`
`many factors, including the desired fluorinated olefin to be
`
`
`
`
`
`
`
`
`produced, the available feedstock, and other specific process-
`
`
`
`
`
`
`
`
`ing constraints, the following Table provides preferred and
`
`
`
`
`
`
`
`
`more preferred ranges of certain process parameters appli-
`
`
`
`
`
`
`
`cable to certain preferred embodiments of the present inven-
`
`
`
`
`
`
`tion (all numerical values in the table are understood to be
`
`
`
`
`
`
`
`
`
`preceded by the word “about.”)
`
`
`
`
`8
`
`that many means and mechanisms are available for control-
`
`
`
`
`
`
`
`
`
`ling the temperature in all subsequent reaction stages, and all
`
`
`
`
`
`
`
`
`such means and mechanisms are within the scope of the
`
`
`
`
`
`
`
`
`
`
`present invention and may be used to control the conversion
`
`
`
`
`
`
`
`
`ofthe reaction stage in accordance with the present inven