Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
1996-07-09
2001-08-14
Knode, Marian C (Department: 1764)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
C502S228000, C502S320000, C570S164000, C570S165000, C570S166000, C570S167000, C570S168000
Reexamination Certificate
active
06274780
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to fluoride compositions, and their preparation and use, and more particularly to chromium and aluminum fluoride catalysts and preparation and use of such catalysts for processing halogenated hydrocarbons.
BACKGROUND
Numerous processes have been developed for changing the fluorine content of halogenated hydrocarbons using chromium containing catalysts. These include increasing the amount of fluorine of halogenated hydrocarbons which are not fully fluorinated, decreasing the fluorine content of halogenated hydrocarbons containing fluorine, and redistributing the number of fluorine atoms among two or more hydrocarbon molecules which are not fully fluorinated.
Various catalysts have been proposed for use in facilitating processes such as hydrofluorination, hydrochlorination (i.e., fluorine substitution by chlorine) and disproportionation which involve halogenated hydrocarbons. See, e.g., L. E. Manzer et al., Adv. Catal. 39, pp. 329-350 (1993). A well known class of art catalysts includes chromium supported on alumina, fluorinated alumina or aluminum fluoride. Typically these materials are prepared by depositing a soluble salt of chromium on an alumina or aluminum fluoride support. While this method does produce a combination catalyst, the support material and the material deposited thereon are not uniformly mixed. Techniques such as coprecipitation which rely upon physical characteristics of individual components (e.g., solubility) also typically yield non-homogeneously dispersed products due to differences in physical and chemical properties of the components. There is an interest in developing means for a more homogeneous dispersion of chromium on an aluminum fluoride support which can be used as a catalyst for changing the fluorine content of halogenated hydrocarbons.
SUMMARY OF THE INVENTION
This invention provides a process for changing the fluorine content of halogenated hydrocarbons containing from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The process is characterized by producing said catalyst by heating a single phase solid catalyst precursor having the formula (NH
3
)
6
Cr
2−x
M
x
F
6
where x is in the range of 0.1 to 1 and M is at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In, to about 400° C. or less to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride.
This invention also provides multiphase catalyst compositions consisting essentially of chromium fluoride and a crystalline fluoride of at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In, provided the atom percent of Cr is at least equal to the atom percent of said crystalline fluoride metals, wherein phases of said crystalline fluorides are homogeneously dispersed with phases of said chromium fluoride. A homogeneously dispersed multiphase catalyst composition consisting essentially of fluorides of chromium and crystalline fluorides of at least one other metal selected from the group consisting of Al, Sc, V, Fe, Ga and In wherein the atom percent Cr is at least equal to the atom percent of said at least one other metal may be prepared in accordance with this invention by heating a corresponding single phase solid catalyst precursor composition of the formula (NH
3
)
6
Cr
2−x
M
x
F
6
wherein M and x are as defined above, to a temperature sufficient to remove essentially all the nitrogen-containing component of said formula composition to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride.
DETAILED DESCRIPTION
The catalytic process of this invention for changing the fluorine content of halogenated hydrocarbons containing from 1 to 6 carbon atoms employs a multiphase catalyst prepared in a manner which provided homogeneous dispersion of multiple metal components by converting a decomposable single phase solid catalyst precursor to a multiple phase catalyst. A single phase catalyst precursor of the formula (NH
3
)
6
Cr
2−x
M
x
F
6
may be prepared by conventional synthetic techniques (e.g., crystallization). Normally, the ratio of the metal components, (2−x):(x), should be between 19:1 and 1:1. Of particular note are compositions where the ratio of Cr to M (e.g., Al) in the precursors is about 1:1 (i.e., x is about 1).
It will be evident that providing single phase precursors as described arranges the two components, Cr and M, in a structured arrangement where Cr and M are closely connected through the NH
3
and F components. As a result of the arrangement of the components in the precursor, when the single phase structure collapses upon heating, uniformly interspersed phases of Cr and M are formed. These are referred to herein as “homogeneously dispersed” phases.
It is desirable to convert the single phase precursor to multiphase composition at a moderately elevated temperature (e.g., about 400° C. or less). While some single phase structures are unstable and collapse upon heating, this conversion is ordinarily accomplished by decomposing the decomposable nitrogen-containing component of the composition. Accordingly, the decomposable nitrogen-containing component preferably decomposes at about 400° C. or less.
The catalysts used for changing the fluorine content of halogenated hydrocarbons should contain fluoride. When the multiphase composition is produced by heating the single phase precursor in air or other oxygen-containing atmosphere (e.g., O
2
) oxyfluorides and/or oxides may be present. These may be at least partially converted to fluoride by contacting the multiphase composition with a vaporizable fluorine-containing fluorinating compound. Typically, where additional fluoride is desired, a multiphase composition is treated with a vaporizable fluorine-containing fluorinating compound such as HF, SF
4
, COF
2
, CCl
3
F, CCl
2
F
2
, CHF
3
or CCl
2
FCClF
2
, at elevated temperatures (e.g., at about 200° C. to about 450° C.) until the desired degree of fluorination is obtained (see, e.g., U.S. Pat. No. 4,902,838).
Included in this invention is a process for increasing the fluorine content of a saturated or olefinic compound having the formula C
n
H
a
F
b
X
c
, wherein n is 1 to 6, a is 0 to 12, b is 0 to 13 and c is 1 to 13, and where each X is independently selected from Cl and Br, by reacting the saturated compounds with HF in the vapor phase. The present invention also provides a process for the disproportionation of a compound having the formula C
p
H
g
F
h
Cl
j
, where p is an integer from 1 to 2, g is an integer from 0 to 3, h is an integer from 1 to 4 and j is an integer from 1 to 3. These processes are respectively characterized by reacting the C
n
H
a
F
b
X
c
compound with HF and conducting the disproportionation of the C
p
H
g
F
h
Cl compound, in the presence of a mutiphase catalyst containing fluorine, which has a phase containing chromium fluoride homogeneously dispersed with a phase containing a fluoride of a metal selected from the group consisting of Al, Sc, V, Fe, Ga, In and mixtures thereof. The mutiphase catalyst containing fluorine can be prepared by heating a corresponding single phase fluoride composition of the formula (NH
3
)
6
Cr
2−x
M
x
F
6
wherein M and x are as defined above, to a temperature sufficient to remove all the nitrogen-containing component of the composition. A more active catalyst may often be achieved by contacting the multiphase composition with a vaporizable fluorine-containing fluorinating compound. Typically, the multiphase composition can be treated with a vaporizable fluorine-containing fluorinating compound such as HF, SF
4
, COF
2
, CCl
3
F, CCl
2
F
2
, CHF
3
or CCl
2
FCClF
2
, at elevated temperatures (e.g., at about 200° C. to about 450° C.). Nevertheless this treatment is not essential.
In one embodiment a homogeneously dispersed multiphase composition consisting of chromium fluoride and beta-AlF
3
is pr
Rao V. N. Mallikarjuna
Subramanian Munirpallam A.
E. I. Du Pont de Nemours and Company
Knode Marian C
Preisch Nadine
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