Process for preparing pentafluoroethane

Details Process for preparing pentafluoroethane Process for preparing pentafluoroethane

1997-03-05

2001-05-15

Siegel, Alan (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Halogen containing

C570S166000

Reexamination Certificate

active

06232514

ABSTRACT:

The present invention relates to a process for preparing pentafluoroethane (HFC-125). More particularly, the present invention relates to a process for preparing HFC-125 by catalytic fluorination with HF of 1,1,1-trifluorodichloroethane (HCFC-123).
It is known that HFC-125, since it does not contain chlorine, has no destructive potential towards the atmospheric ozone and therefore it is an excellent substitute of the conventional chlorofluorocarbons (CFC), which, as known, will be subjected within a few years to severe restrictions both for the production and for the use, according to what provided for by the Montreal Protocol. It is therefore evident the utility of disposing of a process for the manufacture of HFC-125 on industrial scale.
Fluorination processes of tetrachloroethylene with HF in the presence of a catalyst based on an oxide of a transition metal, such as chromium, nickel, cobalt, manganese, etc. (see for isntance U.S. Pat. Nos. 3,258,500, 3,755,477 and 4,766,260), are known in the art. Such processes lead to the achievement of mixtures of more or less fluorinated saturated products, among which 1,1,1-trifluorodichloroethane (HCFC-123), 1,1,1,2-tetra-fluorochloroethane (HCFC-124) and HFC-125. An inconvenience common to such processes is the poor selectivity obtainable in the reactions conditions necessary for producing HFC-125 with satisfactory yields: as a matter of fact, remarkable unrecoverable fractions of disproportionation by-products form, such as CFC-113 (CCl
2
F—CClF
2
and CFC-114 (CClF
2
—CClF
2
). There is also the formation of chloroolefinic by-products, in particular CFC-1112 (CFCl═CFCl) and CFC-1112a (CF
2
═CCl
2
), which, as known, cause problems of toxicity and chemical stability, whereby they must be successively removed. If one tries to optimize the conditions (for instance by falling the reaction temperature) so as to increase the selectivity, the production of HFC-125 decreases unacceptably for an application on industrial scale. Moreover, such processes have the great inceonvenience of a quick decay of the catalytic activity after 70-90 hours of maximum reaction, activity which, even after regeneration of the catalyst, according to known techniques, cannot be restored to the initial values. They are therefore unsuitable processes for continuous productions on industrial scale.
The same problems of decay of the catalytic activity were found by the Applicant for the process described in the patent application EP 349,298, wherein HCFC-123 and/or HCFC-124 are prepared by fluorination of pentahaloethane of formula C
2
HX
5-n
F
n
, where X=Cl, Br, n=0.3, with HF at 250°-450° C., in the presence of a catalyst formed by a metal at oxidation state>0, selected from Cr, Mn, Ni, Rh, Co, supported on a compound essentially formed by Al and F, in ratios corresponding to a content of AlF
3
≧90% by weight. Such a catalyst is prepared according to the following scheme:
(a) soaking of Al
2
O
3
in an aqueous solution of a metal salt;
(b) drying at 100° C. for 18 hours and subsequrent treatment with N
2
at 400° C. to remove any moisture trace;
(c) fluorination with HF, diluted with N
2
, at 450° C., so as to obtain a content in fluorine corresponding to an amount of AlF
3
higher than 90% by weight.
Preferred metals are Ni, Mn and Co.
According to what reported in the above mentioned patent application EP-349,298, the reaction of HCFC-123 with HF leads to the formation of HCFC-124 with good yields, while HFC-125 is present in the final mixture in small amaounts: 7.5% by weight at most with a reaction temperature of 400° C., while operating at 350° C., only 0.5% by weight of HFC-125 is obtained. They are quite unsatisfactory yields for a production of HFC-125 on industrial scale. From such data, it is evident that it is necessary to work at temperatures higher than 400° C., in order to obtain sufficiently high yields in HFC-125. As explained above, this would unavoidably involve the formation of considerable amounts of by-products.
The Applicant has now surprisingly found that by carrying out the fluorination of the HCFC-123 with HF on a catalyst formed by Cr
2
O
3
supported on preformed AlF
3
(i.e. AlF
3
prepared before the addition of the metal catalyst), at a temperature comprised between 310° and 380° C., HFC-125 with high yields (up to 60-70% and over), high conversions (over 80%) and high selectivity, i.e. formation of by-products in very low amounts (50% by moles at most), is obtained. In particular, the chloroolefinic by-products are present in slight amounts, generally lower than 0.05% by moles. Moreover, the catalyst maintains an high activity for a long time even with high organic charges, and can be easily regenerated, for instance with air at high temperature (350°-500° C.).
Object of the present invention is therefore a process for preparing pentafluoroethane (HFC-125), which comprises reacting 1,1,1-trifluorodichloroethane (HCFC-123) with HF at a temperature comprised from 310° to 380° C., preferably from 320° to 350° C., in the presence of a catalyst comprising Cr
2
O
3
supported an preferomed AlF
3
.
The catalyst used in the process object of the present invention can be prepared according to the following method: (a) soaking of AlF
3
in an aqueous solution of a soluble Cr (III) salt (for instance CrCl
3
.6H
2
O); (b) drying, for instance, by air heating at 100-120° C.; (c) activation of the catalyst by air or nitrogen at 200-600° C., preferably from 350° to 500° C., optionally in the presence of steam.
The amount of Cr
2
O
3
is generally comprised from 1 to 15% by weight, calculated as Cr amount with respect to the total weight-of the catalyst.
The support of AlF
3
can be in the form of powder having the particles diameter generally comprised from 20 to 200 &mgr;m, or of pellets. Supports with high surface area, of 25-30 m
2
/g order, are generallay preferred.
The process object of the present invention can be carried out in fixed bed or, preferably, fluid bed reactors.
The HFC-125 can be easily recovered from the mixture flowing out from the reactor by fractional distillation according to known techniques.
The molar ratio between fed HF and HCFC-123 is not a critical parameter and is generally comprised between 1/1 and 10/1, preferably between 1.5/1 and 5/1. The contact times, measured as ratio between the reactants flow in the reaction conditions and the volume of the catalytic bed in rest conditions, are generally comprised from 1 to 20 sec, preferably from 1.5 and 10 sec. The pressure is not a critical parameter: pressures around the atmospheric one or higher pressures are generally used.
The following examples are given for illustrative purposes and not limitative of the scope of the invention itself.


REFERENCES:
patent: 3258500 (1966-06-01), Swamer et al.
patent: 3755477 (1973-08-01), Firth et al.
patent: 4766620 (1988-08-01), Boyhan
patent: 4843181 (1989-06-01), Gumprecht
patent: 4967023 (1990-10-01), Carmello et al.
patent: 5334787 (1994-08-01), Felix et al.
patent: 0 349 298 (1990-01-01), None
patent: 0 408 005 (1991-01-01), None
patent: 0 513 823 (1992-11-01), None

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