Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Patent
1997-07-28
1999-07-06
Yildirim, Bekir L.
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
570177, 585612, 585733, C07C 17093, C07C 1901
Patent
active
059199946
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention relates to supported ruthenium compositions and their use, and more particularly to supported ruthenium catalysts and their use for processing halogenated hydrocarbons.
BACKGROUND
A variety of metal catalysts have been proposed for use in processes for dimerizing chlorine-containing fluorocarbons, for dehalogenating halogenated fluorocarbons for hydrogenolyzing halogenated hydrocarbons and for hydrofluorating halogenated hydrocarbons (see e.g., PCT Publication No. WO 95/05353 for dimerization examples and L. E. Manzer et al., Adv. Catal. (39) pp. 329-350 (1993) for examples of the other listed processes). The products of these processes are useful for the preparation of hydrofluorocarbons which can be substituted for chlorofluorocarbons and hydrochlorofluorocarbons which have been used as refrigerants, blowing agents and cleaning agents. Some of the olefinic products are useful as monomers for fluoropolymers. There is an interest in developing economical processes for the preparation of such compounds.
SUMMARY OF THE INVENTION
This invention provides processes for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a catalyst. The processes are each characterized by employing a catalyst comprising ruthenium on a support selected from the group consisting of (i) fluorided alumina, (ii) aluminum fluoride, and (iii) fluorides of at least one metal selected from the group consisting of Zn, Mg, Ca, Ba, Y, Sm, Eu, and Dy (e.g., zinc fluoride, magnesium fluoride, calcium fluoride, barium fluoride, yttrium fluoride, samarium fluoride, europium fluoride and/or dysprosium fluoride).
This invention further provides multiphase catalyst compositions consisting essentially of ruthenium supported on fluorides of at least one element selected from the group consisting of Zn, Mg, Ca, Ba, Y, Sm, Eu and Dy.
DETAILED DESCRIPTION
The catalytic processes of this invention include processes for dimerizing, processes for dehalogenating, processes for hydrogenolyzing, and processes for increasing the fluorine content of chlorinated fluorocarbons (i.e., compounds containing only carbon, chlorine and fluorine) and chlorinated hydrofluorocarbons (i.e., compounds containing only carbon, hydrogen, chlorine and fluorine). The chlorinated fluorocarbons and chlorinated hydrofluorocarbons can contain from 1 to 6 carbon atoms. The processes employ a supported ruthenium catalyst. The support (i.e., carrier) can be fluorided alumina, aluminum fluoride, zinc fluoride, magnesium fluoride, calcium fluoride, barium fluoride, yttrium fluoride, samarium fluoride, europium fluoride and/or dysprosium fluoride, Fluorided alumina and aluminum fluoride can be prepared as described in U.S. Pat. No. 4,902,838. The other metal fluorides as well as aluminum fluoride can be obtained commercially. The ruthenium can be supported on the carrier by techniques well known in the art such as impregnation. The concentration of ruthenium on the support is typically in the range from about 0.01 to 30 weight percent, and is preferably from about 0.5 to 20 weight percent.
Included in this invention is a process for dimerizing saturated compounds having the formula C.sub.n H.sub.a Cl.sub.b F.sub.c where n is an integer from 1 to 4, a is an integer from 0 to 1, b is an integer from 2 to 9, c is an integer from 0 to 9, where a+b+c equals 2n+2, and where two chlorines that are removed are on the same carbon atom, by reacting said compound with hydrogen in the vapor phase to produce olefins of the formula C.sub.2n H.sub.2a Cl.sub.2b-4 F.sub.2c ; a process for dehalogenating a saturated compound having the formula C.sub.m H.sub.d Cl.sub.e F.sub.f where m is an integer from 2 to 6, d is an integer from 0 to 2, e is an integer from 2 to 4, f is an integer from 3 to 12, where d+e+f equals 2m+2, by reacting said compound with hydrogen in the vapor phase to produce olefins of the formula C.sub.m H.sub.d Cl.sub.e-y F.sub.f-y, where y is an integer fr
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E. I. Du Pont de Nemours and Company
Yildirim Bekir L.
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