Catalyzed halogen exchange between perhaloolefins to form products of the formulas: EQU R.sup.1 R.sup.2 C=CR.sup.3 R.sup.8 and EQU R.sup.5 R.sup.6 C=CR.sup.7 R.sup.4 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.5, Rhu 6l , and R.sup.7 are individually selected from the group F, Cl, Br, C.sub.1 to C.sub.4 perfluoroalkyl, and pentafluorophenyl; or R.sup.1 and R.sup.3, R.sup.2 and R.sup.3, R.sup.5 and R.sup.7, R.sup.6 and R.sup.7 together, with the proviso that both groups are in the cis configuration, are selected from the group perfluoroalkylene of 2 to 4 carbons and EQU o--C.sub.6 F.sub.4 (--)CF.sub.2 --, R.sup.8 =F, R.sup.4 =Cl or Br; and wherein none of the fluoroolefins simultaneously contains both Cl and Br.

BACKGROUND OF THE INVENTION 
This invention concerns transhalogenation between fluoroolefins. This type 
of exchange reaction, a special case of which is known as 
disproportionation, has been employed in the art primarily with 
chlorofluoroalkanes but not with fluoroolefins. One exception, U.S. Pat. 
No. 3,081,358, discloses the disproportionation of alkenes, specifically 
chloropentafluoropropenes, to hexafluoropropene and 
1,1-dichlorotetrafluoropropene-1 in the presence of a specially prepared 
aluminum fluoride catalyst. The catalyst is not employed in the process of 
this invention. 
A number of publications disclose the more common disproportionation of 
chlorofluoroalkanes. Those whcih use an alumina or aluminum fluoride 
catalyst include U.S. Pat. Nos. 3,087,976, 2,767,227, 2,637,748, 
2,478,932, 2,676,996, and 2,478,201. Other catalysts have been employed in 
the disproportionation of alkanes include: 
Alumina activated by pretreatment with a fluorochloroalkane or 
hexafluoropropene: U.S. Pat. Nos. 3,138,559, 3,087,975, and 3,087,974 and 
Japanese Pat. No. 43-27748; 
Aluminum chloride on alumina: U.S. Pat. No. 2,694,739; 
Aluminum fluoride which contains selected amounts of zinc, chromium, nickel 
and iron: U.S. Pat. Nos. 3,973,229, 3,787,331 and 3,650,987; 
Chromiun oxide on activated carbon: E. German Pat. No. 117,444; 
Zinc spinel: Russian Pat. No. 636,216; 
Copper aluminate spinel: Russian Pat. No. 555,080; 
Zirconium tetrachloride: Chem. Abstracts 101, 130215 (1984); 
Zinc, cadmium and mercury: Chem. Abstracts 82, 155162 (1975); 
Copper: Chem. Abstracts 85, 93718 (1976); 
Activated carbon and chromium oxide: U.S. Pat. No. 4,192,822; 
Aluminum fluoride which contains nickel and titanium: U.S. Pat. No. 
4,069,266; 
Chromium fluoride: U.S. Pat. No. 3,651,156; 
Chromium oxyfluoride: G.B. Pat. No. 1,369,870; 
Aluminum chloride: West German Pat. No. 1,618,588; and 
Activated carbon: U.S. Pat. No. 2,981,763. 
SUMMARY OF THE INVENTION 
This invention concerns an improved process for continuously preparing by 
transhalogenation two fluoroolefins of the formula: 
EQU R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.8 
EQU and 
EQU R.sup.5 R.sup.6 C.dbd.CR.sup.7 R.sup.4 
which process comprises reacting at 100.degree.-400.degree. C. at a contact 
time of 0.001-10 seconds, a perhaloolefin of the formula: 
EQU R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.4 
with a perhaloolefin of the formula: 
EQU R.sup.5 R.sup.6 C.dbd.CR.sup.7 R.sup.8 
in the presence of a solid catalyst, as charged to the reactor, selected 
from the group consisting of: 
A. chromium oxide alone or in combination with one or more of Rh.degree., 
Ru.degree., Ir.degree., Pd.degree., Pt.degree., Ag.degree., phosphorus 
oxide, silicon oxide, boron oxide or an oxide or halide of aluminum, 
manganese, zinc, iron, rhodium, nickel, palladium, cobalt, platinum, 
cerium, silver, copper, lead, bismuth, iridium, magnesium, barium, tin, 
lanthanum, calcium, ruthenium, iridium, zirconium, vanadium, molybdenum, 
or tungsten. 
B. aluminum oxide in combination with one or more of Rh.degree., 
Ir.degree., Pd.degree., Pt.degree., Ag.degree., silicon oxide, phosphorus 
oxide, boron oxide or an oxide or halide of manganese, zinc, iron, 
rhodium, nickel, palladium, cobalt, platinum, cerium, silver, copper, 
lead, bismuth, iridium, magnesium, barium, tin, lanthanum, calcium, 
ruthenium, iridium, zirconium, vanadium, molybdenum, or tungsten. 
wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6 and R.sup.7 are 
individually selected from the group F, Cl, Br, C.sub.1 to C.sub.4 
perfluoroalkyl, and pentafluorophenyl; or, R.sup.1 and R.sup.3 together or 
R.sup.2 and R.sup.3 together, or R.sup.5 and R.sup.7 together, or R.sup.6 
and R.sup.7 together, can be selected, when both are in the cis position, 
from the group consisting of perfluoroalkylene of 2 to 4 carbons and 
EQU o--C.sub.6 F.sub.4 (--)CF.sub.2 --, 
i.e. 
##STR1## 
R.sup.8 .dbd.F, R.sup.4 .dbd.Br or Cl; and wherein none of the reactants 
or products simultaneously contain both Cl and Br, and R.sup.1, R.sup.2, 
R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 may be chosen as to 
produce identical structures for the reactants or products.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention provides a process for transhalogenation of 
perhalogenated olefins which is characterized by lower process 
temperatures and increased throughput due to the greatly improved 
catalytic efficiency of the heterogeneous catalysts employed. 
Transhalogenation can be represented by the reaction: 
EQU R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.4 +R.sup.5 R.sup.6 C.dbd.CR.sup.7 
R.sup.8 .revreaction.R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.8 +R.sup.5 
R.sup.6 C.dbd.CR.sup.7 R.sup.4 
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 may be 
chosen such that both R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.4 and R.sup.5 
R.sup.6 C.dbd.CR.sup.7 R.sup.8 are the same molecule. In this case when 
subjected to reaction conditions the molecule produces two distinct 
products for R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.8 and R.sup.5 R.sup.6 
C.dbd.CR.sup.7 R.sup.4. This special case of transhalogenation is referred 
to as disproportionation. In addition R.sup.1, R.sup.2, R.sup.3, R.sup.4, 
R.sup.5, R.sup.6 and R.sup.7 may be chosen such that both R.sup.1 R.sup.2 
C.dbd.CR.sup.3 R.sup.4 and R.sup.5 R.sup.6 C.dbd.CR.sup.7 R.sup.8 
represent two distinct molecules and when subjected to reaction conditions 
would produce identical structures for R.sup.1 R.sup.2 C.dbd.CR.sup.3 
R.sup.8 and R.sup.5 R.sup.6 C.dbd.CF.sup.7 R.sup.4. This special case of 
transhalogenation is referred to as conproportionation. The following 
equations represent particular examples of disproportionation. The reverse 
are examples of conproportionation. 
EQU 2CF.sub.3 C(Cl).dbd.CF.sub.2 .revreaction.CF.sub.3 CF.dbd.CF.sub.2 
+CF.sub.3 C(Cl).dbd.CFCl 
EQU 2CF.sub.2 .dbd.CFCl.revreaction.CF.sub.2 .dbd.CF.sub.2 +CF.sub.2 
.dbd.CCl.sub.2 
In each example of disproportionation, a perhaloolefin more highly 
fluorinated on the carbon-carbon double bond than the starting 
perhaloolefin is obtained. The coproduct obtained is correspondingly less 
fluorinated than the starting perhaloolefin. Subsequent recycle of the 
coproduct by fluorination by known methods, e.g., those disclosed in U.S. 
Pat. No. 3,878,257, will give the starting perhaloolefin which can be 
recycled in the disproportionation reaction. Thus, highly or completely 
fluorinated olefins can be readily obtained by the process of this 
invention. 
As used throughout the specification, the terms "halo" and halide refer to 
F, Cl, and Br. Preferred fluoroolefin products are perfluoroolefins. 
Especially preferred perfluoroolefins are tetrafluoroethylene and 
hexafluoropropylene. Preferred perhaloolefin reactants are those which 
contain up to about 10 carbons, most preferably up to 6 carbons. 
Transhalogenation Catalysts 
Catalysts suitable for charging to the reactor in the process of the 
present invention are solid catalysts comprising supported metals, metal 
oxides or halides preferably selected from transition elements and rare 
earth elements. It is preferable that the chlorides, bromides and 
fluorides of the metal be relatively high melting, i.e., have a melting 
point above about 400.degree. C. The melting points of such chlorides and 
fluorides are given by Glassner, U.S. government publication ANL-5750, 
"The Thermochemical Properties of the Oxides, Fluorides, and Chlorides to 
2500.degree. K.", Argonne National Laboratory. 
Preferred catalysts are those that contain Cr.sub.2 O.sub.3, supported on 
alumina or unsupported, and MnO on alumina. Cr.sub.2 O.sub.3 is 
particularly preferred. 
The term "oxide" and "halide" includes binary, ternary, quaternary, and 
higher polynary oxides and halides as well as solid solutions and 
non-stoichiometric oxides and halides. It includes a single oxide or 
halide; mixed oxides or halides of a single metal in different valence 
states such as FeO and Fe.sub.2 O.sub.3, the corresponding chlorides, and 
the like; as well as mixed oxides or halides of different metals such as 
physical mixtures of iron oxide and manganese oxide, the corresponding 
chlorides, and the like. In the case of ruthenium, rhodium, iridium, 
palladium, platinum, and silver oxides and halides, the terms "oxide" and 
"halide" also refer to the products derived by calcination of such 
compounds, which can be the elemental forms of such metals, either singly 
or in combination with corresponding oxides and halides. 
Representative catalysts of Group A include chromium sesquioxide (Cr.sub.2 
O.sub.3) alone or in combination with one or more of Rh.degree., 
Ru.degree., Ir.degree., Pd.degree., Pt.degree., Ag.degree., iron oxide, 
palladium fluoride, platinum chloride, cobalt oxide, nickel oxide, rhodium 
chloride, rhodium bromide, ruthenium chloride, iridium chloride, copper 
oxide, phosphorus pentoxide, boron oxide, barium oxide, lanthanum oxide, 
calcium oxide, zirconium oxide, cerium oxide, silver fluoride, copper 
oxide, copper chloride, manganese oxide, lead oxide, bismuth oxide, 
iridium chloride, magnesium oxide, silicone dioxide, tin oxide, vanadium 
oxide, molybdenum oxide or tungsten oxide. 
Representative catalysts of Group B are aluminum oxide in combination with 
one or more of Rh.degree., Ru.degree., Ir.degree., Pd.degree., Pt.degree., 
Ag.degree., magnanese oxide, silicon dioxide, zinc oxide, zinc chloride, 
iron oxide, iron chloride, rhodium chloride, nickel chloride, nickel 
oxide, palladium oxide, palladium chloride, palladium fluoride, cobalt 
oxide, platinum chloride, platinum oxide, cerium oxide, silver fluoride, 
silver bromide, copper oxide, copper chloride, lead oxide, bismuth oxide, 
iridium chloride, phosphorus pentoxide, magnesium oxide, boron oxide, 
barium oxide, tin oxide, lanthanum oxide, calcium oxide, ruthenium oxide, 
iridium chloride, zirconium oxide, vanadium oxide, molybdenum oxide, or 
tungsten oxide. 
Catalyst Preparation 
The catalysts employed in the process of the present invention can be made 
by any conventional or suitable method in the art including evaporation, 
impregnation or precipitation, each followed by calcination. In the 
evaporation method, the desired components are mixed together with water 
to form a slurry or solution. The water is evaporated and the resultant 
solid is then dried and calcined. This method is of value where unwanted 
materials are not present and a washing step is not needed. 
In the impregnation method, a solution of an active component or components 
is contacted with a support to thoroughly wet it. An excess of the 
impregnating solution is generally used and when the support is thoroughly 
saturated, the excess solution is removed, as by filtration or 
decantation. The impregnated support is then dried and subjected to 
calcination. 
In the precipitation method, aqueous solutions of desired constituents are 
mixed with a solution of a precipitating agent. A variety of bases or 
base-forming compounds can be used as precipitating agents, including 
aqueous ammonia, ammonium carbonate, ammonium bicarbonate, urea and the 
like. The presence of impurities in the final catalyst is minimized by 
carrying out the precipitation with dilute solutions and by using ammonia 
or ammonium salts as the precipitant along with nitrates of the desired 
metals. The resulting precipitate then requires a minimum of washing since 
any absorbed material remaining can be removed in the subsequent 
calcination step. 
In the calcination step which decomposes salts such as carbonate or 
nitrates to oxides, the catalyst material is heated in air to a 
temperature which is generally below 500.degree. C. The calcination is 
usually carried out for several hours. The process of this invention is 
carried out in the gase phase using well-known chemical engineering 
practices, which include continuous, semi-continuous, and batch operation. 
Preferably, the catalysts employed in the process of the present invention 
are activated prior to use. Activation can be achieved by preheating the 
catalyst at a relatively high temperature, e.g., about 300.degree. to 
400.degree. C., with a fluorooledin, for a period ranging from 1 minute to 
1 hour. Activation is conveniently carried out in a flow system by passing 
the fluoroolefin over the catalyst contained in the reactor tube. 
Specific fluoroolefins suitable for use in activation of the catalyst 
include tetrafluoroethylene, chlorotrifluoroethene, 
1,1-dichloro-2,2-difluoroethane, hexafluoropropene, perfluoro-1-butene and 
perfluoro-2-butene. After activation, the catalysts can be efficiently 
employed at at temperatures as low as about 100.degree. C. 
It is not necessary that the catalyst have a high surface area. For 
instance, a Cr.sub.2 O.sub.3 catalyst with a surface area as low as about 
5 m.sup.2 /g is suitable. It is preferred, however, that catalysts 
supported on alumina have a surface area greater than about 200 m.sup.2 
/g. 
Process Conditions 
Preferred reaction temperatures are about 100.degree. to 400.degree. C. 
Pressures are about 10.sup.-3 to 10 MPa, preferably about 0.1 MPa. Contact 
times are preferably about 0.001 to 10 seconds. 
It is preferred to operate a nonoxidative atmosphere in which molecular 
oxygen or similar oxidizing gases are absent. Generally, this results in 
fewer undesired by-products. The process is preferably carried out without 
any diluent but an inert atmosphere of nitrogen, helium, argon, neon, and 
the like can be used. 
Contact time of the prehaloolefins with the catalyst can vary over a wide 
range depending upon reaction temperature, pressure, process dynamics, and 
the reactants and catalysts employed. For example, in a continuous flow 
process, a contact time as short as about 0.001 sec can be employed. 
Generally, longer contact times are employed at lower temperatures. 
When a continuous flow process is employed, contact time is calculated 
using the following equation. 
##EQU1## 
The transhalogenation process of the invention is conveniently carried out 
at atmospheric pressure, although either higher or lower pressures can be 
employed. The type of reactor vessel is not critical so long as it is able 
to withstand the temperatures and pressures employed. Corrosion resistant 
materials such as nickel-based corrosion resistant alloys (Hastelloy) and 
tantalum are preferred. The catalyst can be used in a fixed bed or a 
fluidized bed configuration. 
After transhalogenation reaction has been completed, the reaction products 
can be separated by such conventional procedures as distillation, 
extraction by a solvent, adsorption, or other suitable techniques. Any 
portion of the starting perhaloolefins that is not reacted can be 
recycled. 
EXAMPLES 
The following Examples illustrate the invention. All parts and percentages 
are by weight, and all degrees are Celsius unless otherwise noted. 
Preferred embodiments are represented by Examples 63 and 64. 
General Procedure 
A designated quantity of catalyst was charged to a 1-cm 
diameter.times.10-cm long glass reactor (Vycor.RTM.) which was heated in a 
tube furnace. When indicated, the catalyst was activated by heating at an 
elevated temperature for a designated time in a stream of 
hexafluoropropene. The reactor was then cooled to the temperature selected 
for reaction. Flow rates of gases were measured with a mass flow 
controller calibrated with tetrafluoroethylene. The feeds of 
perhaloolefins were started together with a feed of nitrogen is one was 
used. The product stream was transported directly to a gas chromatograph 
and analyzed on a 2.44 m.times.0.32 cm (8'.times.1/8") column of 1% of 20M 
molecular weight polyethylene glycol capped with nitroterephthalic acid on 
activated carbon, programmed as follows: 50.degree. for 3 min; temperature 
raised at 20.degree./min to 150.degree.; hold for 2 min; temperature 
raised at 35.degree./min to 200.degree.; helium flow rate 20 mL/min. 
Product compositions are expressed in area percent with a flame ionization 
detector. 
If transhalogenation was not observed at this initial reaction temperature, 
the temperature was raised until reaction was observed. If conversion of 
perhaloolefins was complete at the initial temperature, the temperature 
was lowered until partial conversion was obtained. 
As used in the Examples, the following abbreviations for fluoroolefins and 
fluoroalkanes apply: 
FC-114: 1,2-Dichlorotetrafluoroethane; CF.sub.2 ClCF.sub.2 Cl 
FC-115: Chloropentafluoroethane; ClCF.sub.2 CF.sub.3 
FC-1110: Tetrachloroethane; (Cl).sub.2 C.dbd.C(Cl).sub.2 
FC-1111: Fluorotrichloroethane; F(Cl)C.dbd.C(Cl).sub.2 
FC-1112a: 1,1-Dichloro-2,2-difluoroethene; F.sub.2 C.dbd.C(Cl).sub.2 
FC-1112: 1,1-Dichloro-1,2-difluoroethene; F(Cl)C.dbd.C(Cl)F 
FC-1113: Chlorotrifluoroethene; CF(Cl).dbd.CF.sub.2 
FC-1114: Tetrafluoroethene; CF.sub.2 .dbd.CF.sub.2 
FC-216: 1,2-Dichlorohexafluoropropane; CF.sub.3 CFClCF.sub.2 Cl 
FC-1211: 3-Fluoropentachloro-1-propene; CFCl.sub.2 C(Cl).dbd.CCl.sub.2 
FC-1212: 3,3-Difluorotetrachloro-1-propene; CF.sub.2 ClC(Cl).dbd.CCl.sub.2 
FC-1213: 1,1,2-Trichloro-3,3,3-trifluoro-1-propene; CF.sub.3 
C(Cl).dbd.CCl.sub.2 
FC-1214: 1,1-Dichloro-1,3,3,3-tetrafluoro-1-propene; CF.sub.3 
C(Cl).dbd.CFCl 
FC-1215: 2-Chloropentafluoropropene; CF.sub.3 C(Cl).dbd.CF.sub.2 
FC-1216: Hexafluoropropene; CF.sub.3 CF.dbd.CF.sub.2 
Catalyst Preparation 
Two general methods were used to prepare the catalysts used in the 
Examples: coevaporation and incipient wetness impregation. 
Method A: Coevaporation 
Each of the soluble inorganic salts was dissolved in water and the aqueous 
solutions were combined. The resulting solution was placed on a hot plate 
and the water was boiled off. The dry solid was then calcined in a furnace 
at 200.degree. for 1 hr, and then at 400.degree. for 1 hr. In the 
preparation of the catalyst of Example 38, 10% CrF.sub.3 /Al.sub.2 
O.sub.3, a solution of 73 g of hydrated aluminum nitrate, 3.7 g of 
hydrated chromium nitrate and 1 g of ammonium fluoride was heated to 
dryness, and the residue was calcined. 
Method B. Impregnation 
First, the pore volume of the support was determined by how much water 
could be absorbed into its pore structure. Then, a solution of the salt to 
be impregnated was dissolved in this calculated amount of water, and the 
solid support was added. The moist supported catalyst was calcined at 
100.degree. for 1 hr, at 200.degree. for 1 hr. and finally at 400.degree. 
for 1 hr. In the preparation of the catalyst, 10% CrF.sub.3 /Cr.sub.2 
O.sub.3, chromium oxide was found to adsorb 0.5 g of water/g of oxide. A 
solution of 0.5 g of ammonium fluoride in 2.5 mL of water was added to 5 g 
of Cr.sub.2 O.sub.3. The solid catalyst was then calcined. 
Catalyst preparations are summarized in Table 1. All preparations were by 
coevaporation except where noted by (B). 
TABLE 1 
______________________________________ 
Catalyst Catalyst 
Composition Composition 
______________________________________ 
10% InCl.sub.3 /Al.sub.2 O.sub.3 
2% PdF.sub.2 /Al.sub.2 O.sub.3 
10% CrCl.sub.3 /Al.sub.2 O.sub.3 
1% CrF.sub.3 /Cr.sub.2 O.sub.3 
2% PdCl.sub.2 /Cr.sub.2 O.sub.3 
10% NiF.sub.2 /Al.sub.2 O.sub.3 
20% Ce.sub.2 O.sub.3 /Al.sub.2 O.sub.3 
9% CrF.sub.3 /Cr.sub.2 O.sub.3 
20% CoCl.sub.2 /Al.sub.2 O.sub.3 
1% NiF.sub.2 /Cr.sub.2 O.sub.3 
Cr.sub.2 O.sub.3 
3% NiF.sub.2 /Cr.sub.2 O.sub.3 
10% MnO/Cr.sub.2 O.sub.3 
9% NiF.sub.2 /Cr.sub.2 O.sub.3 
10% Al.sub.2 O.sub.3 /Cr.sub.2 O.sub.3 
10% B.sub.2 O.sub.3 /Al.sub.2 O.sub.3 
10% CoO/Cr.sub.2 O.sub.3 
20% MgCl.sub.2 /Al.sub.2 O.sub.3 
10% Fe.sub.2 O.sub.3 /Cr.sub.2 O.sub.3 
10% P.sub.2 O.sub.5 /Cr.sub.2 O.sub.3 
10% NiO/Cr.sub.2 O.sub.3 
10% B.sub.2 O.sub.3 /Cr.sub.2 O.sub.3 
1% Pd/Cr.sub.2 O.sub.3 
10% CaCl.sub.2 /Cr.sub.2 O.sub.3 
10% CrF.sub.3 /Al.sub.2 O.sub.3 
10% BaO/Cr.sub.2 O.sub.3 
10% MnF.sub.2 /Al.sub.2 O.sub.3 
10% SnCl.sub.2 /Al.sub.2 O.sub.3 
10% CuF.sub.2 /Al.sub.2 O.sub.3 
10% ZnCl.sub.2 /Al.sub.2 O.sub.3 
10% FeF.sub.3 /Al.sub.2 O.sub.3 
10% La.sub.2 O.sub.3 /Al.sub.2 O.sub.3 
10% ZnF.sub.2 /Al.sub.2 O.sub.3 
10% La.sub.2 O.sub.3 /Cr.sub.2 O.sub.3 
10% CeF.sub.3 /Al.sub.2 O.sub.3 
10% ZrO.sub.2 /Cr.sub.2 O.sub.3 
10% CuO/Cr.sub.2 O.sub.3 
10% ZrO.sub.2 /Al.sub.2 O.sub.3 
10% MnO/Cr.sub.2 O.sub.3 
10% CaO/Cr.sub.2 O.sub.3 
1% Pd/Cr.sub.2 O.sub.3 
10% Cr.sub.2 O.sub.3 /Al.sub.2 O.sub.3 --SiO.sub.2 (B) 
10% CoF.sub.2 /Al.sub.2 O.sub.3 
10% Cr.sub.2 O.sub.3 /TiO.sub.2 --Al.sub.2 O.sub.3 (B) 
3% CrF.sub.3 /Cr.sub.2 O.sub.3 
10% Cr.sub.2 O.sub.3 /ZrO.sub.2 (B) 
10% CrF.sub.3 /Cr.sub.2 O.sub.3 (B) 
______________________________________ 
Comparative Experiment 
In order to provide a standard against which the catalysts and processes of 
the present invention could be evaluated, a reaction substantially similar 
to those conducted as examples of the invention was conducted using 
AlF.sub.3 as catalyst. The AlF.sub.3 catalyst employed was a commercial 
catalyst marketed under the trade name Harshaw.RTM. Al-1101. 
A total of 8.0 g of AlF.sub.3 catalyst was charged, and the reactor was 
heated to an initial temperature of 400.degree.. Approximately equimolar 
streams of liquid FC-1213, 1 mL/hr, and gaseous FC-1216, 5 mL/min, and 
nitrogen (10 mL/min) were started, and the products were analyzed 
initially on the G.C. column, as follows: FC-1216, 46%; FC-1215, 0.9%; 
FC-1214, 2.9%; FC-1213, 47%. 
Example 1 
A total of 5.3 g of Cr.sub.2 O.sub.3 catalyst (Newport Chrome) was charged, 
and the reactor was heated to an initial temperature of 350.degree.. 
Approximately equimolar streams of liquid FC-1213, 1 mL/hr, and gaseous 
FC-1216, 5 mL/min, and nitrogen (20 mL/min) were started, and the products 
were analyzed initially on the G.C. column, as follows: FC-1216, 23%; 
FC-1215, 40%; FC-1214, 26%; FC-1213, 3%. 
The reactor temperature was lowered progressively, and transhalogenation 
was continued. At 90.degree., with the same flow rates of FC-1213 and 
FC-1216 but with a nitrogen flow rate of 80 mL/min (calculated contact 
time of 0.7 sec), the product composition was 16% FC-1216; 35% FC-1215; 9% 
FC-1214; 39% FC-1213. 
Examples 2 to 59 
These Examples show a variety of cataysts which can be employed in the 
transhalogenation reaction: 
##STR2## 
The reactions were carried out by the General Procedure set forth above, 
with the following additional qualifications. Feed rates of 1 mL/hr of 
liquid FC-1213 and 5 mL/min of gaseous FC-1216 were used. Examples 2 to 4 
used a nitrogen stream of 10 mL/min, and in Examples 5 to 32 and 40 to 42 
a stream of nitrogen of 5 mL/min was used. No nitrogen was used in 
Examples 33 to 39 and 43 to 59. The catalysts used in Examples 12 to 59 
were activated by pretreatment with a stream of FC-1216 (5 mL/min) at 
400.degree. for 15 min (Examples 12 to 14) or 10 min (Examples 15 to 59). 
The specific cataysts used, initial temperatures (T.sub.i), reaction 
temperatures (T.sub.i), and product compositions are summarized in Table 
2, below. 
TABLE 2 
__________________________________________________________________________ 
Temperature 
Product Analysis 
Ex. 
Catalyst, g T.sub.i /T.sub.r (.degree.C.) 
FC-1216 
FC-1215 
FC-1214 
FC-1213 
__________________________________________________________________________ 
2 57% MgO/Al.sub.2 O.sub.3, 4.7 
300/400 
32 20 14 32 
3 19% Cr.sub.2 O.sub.3 /Al.sub.2 O.sub.3, 7.6 
400/200 
17 34 23 26 
4 33% Cr/Si--Al/O, 5.0 
400/200 
19 42 31 9 
5 3% each of Ni,Co, 
300/250 
29 35 14 22 
Fe oxides/Al.sub.2 O.sub.3, 7.0 
6 20% FeO/Al.sub.2 O.sub.3 
300/200 
39 20 4 36 
7 14% NiO/Al.sub.2 O.sub.3, 5.0 
300/200 
36 22 10 32 
8 20% FeCl.sub.3 /Al.sub.2 O.sub.3, 5.0 
300/200 
24 39 26 8 
9 10% MoO.sub.3 /Al.sub.2 O.sub.3, 5.0 
300/300 
47 28 16 7 
10 10% WO.sub.3 /Al.sub.2 O.sub.3, 7.0 
300/300 
45 25 7 3 
11 10% MnO/Al.sub.2 O.sub.3, 5.8 
300/200 
45 14 9 30 
12 10% InCl.sub.3 /Al.sub.2 O.sub.3, 2.5 
300/200 
32 24 8 31 
13 0.5% Pt/Al.sub.2 O.sub.3, 5.0 
300/200 
35 15 3 38 
14 0.5% Pd/Al.sub.2 O.sub.3, 5.0 
300/200 
40 10 2 39 
15 10% each ZnO/Cr.sub.2 O.sub.3 / 
300/200 
18 34 25 11 
Al.sub.2 O.sub.3, 5.0 
16 1% FeO/Cr.sub.2 O.sub.3, 2.0 
150/150 
31 32 10 26 
17 1% PdCl.sub.2 /Cr.sub.2 O.sub.3, 2.0 
150/250 
44 4 11 38 
18 1% Pt/Cr.sub.2 O.sub.3, 2.0 
150/150 
41 11 4 43 
19 1% CoCl.sub.2 /Cr.sub.2 O.sub.3, 2.0 
150/150 
33 5 1 61 
20 20% CoCl.sub.2 /Al.sub.2 O.sub.3, 2.0 
150/200 
39 20 6 35 
21 20% Ce.sub.2 O.sub.3 /Al.sub.2 O.sub.3, 2.0 
150/300 
49 8 2 40 
22 24% ZnO/Al.sub.2 O.sub.3, 5.0 
150/300 
47 10 2 40 
23 10% Ag/Al.sub.2 O.sub.3, 2.0 
150/300 
45 13 8 33 
24 10% CrCl.sub.3 /Al.sub.2 O.sub.3, 1.0 
150/300 
30 32 17 21 
25 10% Al.sub.2 O.sub.3 /Cr.sub.2 O.sub.3, 1.0 
200/300 
24 31 18 23 
26 10% NiO/Cr.sub. 2 O.sub.3, 1.0 
200/200 
17 42 29 12 
27 10% CoO/Cr.sub.2 O.sub.3, 1.0 
200/200 
45 12 2 4 
28 10% Fe.sub.2 O.sub.3 /Cr.sub.2 O.sub.3, 1.0 
200/300 
23 31 26 19 
29 10% FeF.sub.3 /Al.sub.2 O.sub.3, 2.0 
300/300 
31 40 19 10 
30 10% CuF/Al.sub.2 O.sub.3, 2.0 
300/300 
51 10 3 35 
31 10% ZnF.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
40 34 17 3 
32 10% CeF.sub.3 /Al.sub.2 O.sub.3, 2.0 
300/300 
65 20 6 5 
33 10% MnF.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
13 26 34 21 
34 10% NiF.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
19 38 29 10 
35 2% PdF.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
33 26 17 19 
36 10% CuO/Cr.sub.2 O.sub.3, 1.0 
200/300 
27 46 23 4 
37 10% CrF.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
63 22 3 10 
38 9% CrF.sub.3 /Cr.sub.2 O.sub.3, 2.0 
300/300 
15 45 33 7 
39 3% CrF.sub.3 /Cr.sub.2 O.sub.3, 2.0 
300/150 
18 44 21 17 
40 3% NiO/Cr.sub.2 O.sub.3, 1.0 
200/300 
16 41 28 15 
41 9% NiO/Cr.sub.2 O.sub.3, 1.0 
200/200 
12 45 36 6 
42 10% CoF.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
20 41 32 6 
43 10% PbO/Al.sub.2 O.sub.3, 2.0 
300/300 
25 28 21 26 
44 10% Bi.sub.2 O.sub.3 /Al.sub.2 O.sub.3, 2.0 
300/300 
24 29 24 22 
45 10% P.sub.2 O.sub.5 /Cr.sub.2 O.sub.3, 2.0 
300/200 
13 41 36 10 
46 20% MgCl.sub.2 /Al.sub.2 O.sub.3, 2.0 
300/300 
47 5 1.4 45 
47 10% B.sub.2 O.sub.3 /Al.sub.2 O.sub.3, 2.0 
300/300 
47 3 2 47 
48 10% B.sub.2 O.sub.3 /Cr.sub.2 O.sub.3, 2.0 
300/200 
9 41 42 7 
49 10% BaO/Cr.sub.2 O.sub.3, 1.0 
300/300 
10 40 38 11 
50 10% SnCl.sub.2 /Al.sub.2 O.sub.3, 3.0 
300/300 
47 7 3 42 
51 10% ZnCl.sub.2 /Al.sub.2 O.sub.3, 3.0 
300/300 
22 41 19 17 
52 10% La.sub.2 O.sub.3 /Al.sub. 2 O.sub.3, 3.0 
300/300 
42 14 7 36 
53 10% La.sub.2 O.sub.3 /Cr.sub.2 O.sub.3, 2.0 
300/300 
11 44 39 6 
54 10% CaO/Cr.sub.2 O.sub.3, 2.0 
300/300 
41 14 8 36 
55 91% SiO.sub.2 /Al.sub.2 O.sub.3, 5.0 
300/300 
56 10 2 28 
56 10% Cr.sub.2 O.sub.3 /Si--Al--O, 4.0 
300/300 
8 37 44 8 
57 98% ZrO.sub.2 /Al.sub.2 O.sub.3, 5.0 
300/300 
63 4 -- 28 
58 Cr--Y Zeolite, 3.0 
300/300 
21 42 22 14 
59 10% ZrO.sub.2 /Cr.sub.2 O.sub.3, 3.0 
300/400 
39 12 5.4 41 
__________________________________________________________________________ 
Example 60 
Tetrafluoroethylene+FC 1213. Reaction was carried out by the General 
Procedure using 5 g of the Cr.sub.2 O.sub.3 catalyst of Example 1, 5 
mL/min of gaseous tetrafluoroethylene (TFE), 0.5 mL/hr of liquid FC-1213, 
and 20 mL/min of nitrogen. The initial reaction temperature was 
100.degree. and the temperature was raised eventually to 250.degree.. 
Reaction started at 100.degree.. At 150.degree., the product composition 
was 23% TFE, 21% chlorotrifluoroethene, 30% FC-1215, 15% 
dichlorodifluoroethene, 5% FC-1214, and 3% FC-1213. 
Example 61 
Disproportionation of Chlorotrifluoroethene. Reaction was carried out by 
the General Procedure using 7 g of the Cr.sub.2 O.sub.3 catalyst of 
Example 1, 5 mL/min of gaseous chlorotrifluoroethene, and 20 mL/min of 
nitrogen. The initial temperature was 150.degree.. At 250.degree., the 
product composition was 8% TFE, 72% chlorotrifluoroethene, and 13% 
dichlorodifluoroethene. 
Example 62 
Disproportionation of FC-1214. Reaction was carried out by the General 
Procedure using 8 g of the Cr.sub.2 O.sub.3 catalyst of Example 1, 0.5 
mL/hr of liquid FC-1214 (with cooling of the syringe), and 20 mL/min of 
nitrogen. The initial temperature was 100.degree.. At 200.degree., the 
product composition was 67% FC-1214, 11% FC-1213, 21% FC-1215, and 0.6% 
FC-1216. 
Example 63 
Disproportionation of FC-1215. Reaction was carried out by the General 
Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst, 4 mL/min of gaseous 
FC-1215, and 10 mL/min of nitrogen. The initial temperature was 
250.degree.. At 100.degree. and 20 mL/min of nitrogen, the product 
composition was 17% FC-1216, 55% FC-1215, 23% FC-1214, and 5% FC-1213. 
Example 64 
Disproportionation of Chlorotrifluoroethene. Reaction was carried out by 
the General Procedure using 15 g of Cr.sub.2 O.sub.3 catalyst, 5 mL/min of 
nitrogen, and 5 mL/min of chlorotrifluoroethene at various temperatures. 
The results are summarized in Table 3, below, in which the products are 
shown in area percent as determined by GC/MS. Disproportionation was 
reasonably complete at 180.degree. to give FC-1114 (CF.sub.2 
.dbd.CF.sub.2) and FC-1112 (CF.sub.2 .dbd.CCl.sub.2). 
TABLE 3 
______________________________________ 
Product Analysis 
Temp FC- 
(.degree.C.) 
1114 FC-115 FC-1113 
FC-1112a 
FC-1112 
FC-1111 
______________________________________ 
180 17 0.8 58 9.5 11.8 1.2 
200 18 1.2 56 10 12 1.4 
230 15 9.9 37 20 7 3.1 
250 11 18 25 28 4 5 
______________________________________ 
Example 65 
Disoproportionation of 1-Bromo-1,2,2-trifluoroethene. Reaction was carried 
out by the General Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst, 5 
mL/min of gaseous 1-bromo-1,2,2-trifluoroethene, and 5 mL/min of nitrogen. 
The initial temperature was 250.degree.. At 300.degree., the product 
composition was shown to contain CF.sub.2 .dbd.CBr.sub.2 by nmr analysis. 
GC analysis of the gas stream on-line showed 3 assignable peaks: FC-1114 
(9.7 area %); CF.sub.2 .dbd.CFBr (32 area %); and CF.sub.2 .dbd.CBr.sub.2 
(32 area %). Small amounts of perhaloalkanes were seen in both the GC and 
NMR. 
Example 66 
TFE+1,1-Dichloro-2,2-difluoroethene. Reaction was carried out by the 
General Procedure using 10 g of Cr.sub.2 O.sub.3 catalyst and the 
designated amounts of gaseous TFE and gaseous 
1,1-dichloro-2,2-difluoroethene. The initial temperature was 275.degree.. 
Reaction products are summarized in Table 4, below. 
TABLE 4 
______________________________________ 
Feed Rate Product Analysis 
Temp. mL/min FC- 
(.degree.C.) 
1114 1112 1114 115 1113 114 1112 1111 
______________________________________ 
275 5 5 7.1 12.2 10.6 7.7 33 5.7 
275 6 4 16.5 8 9.8 9.3 29 5.3 
275 4 6 14.4 5 7 7 41 8.2 
300 5 5 9.6 9.4 16.3 7.2 33 6.4 
250 5 5 29 2.0 11.4 3.3 44 4.3 
______________________________________ 
Example 67 
TFE+1,2-Dichloro-1,2-difluoroethene. The procedure of Example 66 was 
employed except that 1,1-dichloro-2,2-difluoroethene was replaced with 
1,2-dichloro-1,2-difluoroethene (5 mL/min). The inital temperature was 
275.degree.. GC analysis showed the following principal products. Area 
percents are noted in parentheses: FC-114 (26); FC-115 (9.6); FC-1113 
(31); FC-114 (12.3); FC-1112 (10.6); FC-1111 (0.9). 
Example 68 
FC-1216+Tetrachloroethene. Reaction was carried out by the General 
Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst, activated by heating in 
a stream FC-1216 (5 mL/min) at 100.degree. for 0.5 hr. Nitrogen (5 mL/min) 
and liquid tetrachlorethene (5 mL/hr) streams were started. After 0.5 hr, 
the temperature was raised to 400.degree.. The results obtained at several 
temperatures are summarized in Table 5, below. 
TABLE 5 
______________________________________ 
FC- FC- 
Temp 1216 FC-1215 FC-1214 
FC-1112 
1111 FC-1110 
______________________________________ 
400 24 11 3 1.4 5.3 54 
400(1) 
14 6.5 2.2 1.3 4.8 70 
400(2) 
70 13 1.6 1.6 1.8 11 
300(3) 
45 16 15 1.7 1.3 14.4 
350(1) 
22 12 4 2.7 4.2 48 
______________________________________ 
(1) Tetrachloroethene flow rate was 1.5 mL/hr 
(2) Tetrachloroethene flow rate was 0.6 mL/hr 
(3) FC1216, 10 mL/min; tetrachloroethene, 1 mL/hr 
Example 69 
1,1-Dichloro-2,2-difluoroethene+Tetrachloroethene. Reaction was carried out 
by the General Procedure using 10 g of Cr.sub.2 O.sub.3 catalyst with no 
activation. Nitrogen (5 ml/min), liquid tetrachloroethane (1 ml/hr), and 
gaseous 1,1-dichloro-2,2-difluoroetheene (7 to 10 ml/min) were passed over 
the catalyst at 330.degree.. The principal product formed was 
fluorotrichloroethene. 
Example 70 
FC-1213+Octafluoro-2-butene. Reaction was carried out by the General 
Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst activated by heating in a 
stream of gaseous octafluoro-2-butene (5 ml/min) at 400.degree. for 10 
min. The reactor temperature was lowered to 300.degree., and a stream of 
liquid FC-1213 (1 mL/hr) was started. The temperture was lowered to 
200.degree. and the product stream was analyzed. NMR analysis of the 
product showed the presence of FC-1213, FC-1214, and FC-1215 in the molar 
ratio of 60:21:18. Both perfluoro-cis- and perfluoro-trans-2-butene were 
present as well as the corresponding compounds with one or both or the 
vinyl fluorines replaced by chlorine, i.e. CF.sub.3 CF.dbd.C(Cl)CF.sub.3 
and CF.sub.3 C(Cl).dbd.C(Cl)CF.sub.3. The ratio of butenes with 2:1:0 
chlorine atoms was 31:29:31. 
Example 71 
FC-1213+Hexafluorocyclobutene. Reaction was carried out by the General 
Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst, activated by heating in 
a stream of gaseous hexafluorocyclobutene (5 mL/min) at 400.degree. for 10 
min. The reactor temperature was lowered to 300.degree., and a stream of 
liquid FC-1213 (1 mL/hr) was started. The reaction temperature was lowered 
to 200.degree., and a liquid sample was collected and analyzed by NMR. The 
following products were identified: FC-1213, FC-1214, l and FC-1215 in the 
molar ratio of 41:22:37; hexafluorocyclobutene, 
1-chloropentafluorocyclobutene, and 1,2-dichlorotetrafluorocyclobutene in 
the molar ratio of 8:39:54. 
Example 72 
FC-1213+Octafluorocyclopentene. Reaction was carried out by the General 
Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst, activated by heating in 
a stream of gaseous octafluorocyclopentene (5 mL/min) at 400.degree. for 
10 min. The reactor temperature was lowered to 300.degree., and a stream 
of liquid FC-1213 (1 mL/hr) was started. The reaction product was analyzed 
by fluorine nmr. The following products were identified: equimolar amounts 
of FC-1213, FC-1214, and FC-1215; equimoar amounts of 
octafluorocyclopentene, 1-chloroheptafluorocyclopentene, and 
1,2-dichlorohexafluorocyclopentene. 
Example 73 
FC-1213+Perfluoro-4-methyl-2-pentene. Reaction was carried out by the 
General Procedure using 5 g of Cr.sub.2 O.sub.3 catalyst, activated by 
heating in a stream of gaseous FC-1216 (5 mL/min) and nitrogen (5 mL/min) 
at 400.degree. for 10 min. The reactor temperature was lowered to 
300.degree. and the FC-1216 stream was discontinued. A stream of liquid (1 
mL/hr) consisting of an equimolar mixture of FC-1213 and 
perfluoro-4-methyl-2-pentene was started. GC/MS showed the presence of 4 
isomers of C.sub.6 F.sub.11 Cl and NMR showed the presence of FC-1213, 
FC-1214, and FC-1215 in the molar ratio of 12:5:1.