Title of Invention

A PROCESS FOR PRODUCING CHLOROFLUROCARBONS

Abstract

The present invention relates to a process for producing CF3CC12CF3 comprising: contacting a saturated C-3 reactant comprising one or more of perhydrogenated or partially halogenated C-3 hydrocarbons with C12 and HF in the presence of a first catalyst at a first temperature to form a C-3 product comprising a C-3 perhalogenated compound, wherein the first catalyst comprises chromium; and contacting the C-3 product with HF in the presence of a second catalyst at a second temperature different from the first temperature to form CF<SUB>3</SUB>CC<SUB>12</SUB>CF<SUB>3</SUB> wherein the second temperature is greater than 300°C.

Full Text

FIELD OF INVENTION The present invention is directed to production methods, as well as, synthetic and separation methods. More particularly, the present invention is directed to methods for manufacturing selective isomers of chlorofluorocarbons and hydrofluorocarbons from aliphatic, olefinic or partially halogenated hydrocarbons. BACKGROUND OF THE INVENTION- Since the beginning of global warming concerns, chlorofluorocarbon manufacturers have had to produce compounds that perform substantially the same as fully halogenated chlorofluorocarbons without the adverse environmental impact. Only through the introduction of these new compounds have their environmental impact been completely understood. In certain instances, some of these new compounds have been removed from the marketplace. These types of issues make the flooding agent, extinguishant, propellant and refrigerant production industry a dynamic and ever-changing marketplace where processes for the production of chlorofluorocarbons and fluorocarbons are advancing quickly to accommodate both environmental as well as economical requirements. Some useful compounds in this area include both saturated and unsaturated fluorocarbons, such as 1,1,1.2,3,3,3-heptafluoropropane (CF3-CFH-CF3, HFC-227ea), 1,1,1,2,2,3,3-heptafluoropropane (CF3-CF2-CHF2, HFC-227ca) and hexafluoropropane (hexafluoropropylene, HFP, CF3-CF=CF2, FC-1216). One well known method of synthesizing these compounds begins with the chlorofluorination of propane, propylene or partially halogenated C-3 hydrocarbons with hydrogen fluoride (HF) and chlorine (CI:) in the presence of a metal-containing solid catalyst. Examples of this chlorofluorination step can be found in U.S. Patents 5,057,634 and5,043,491 to Webster. As taught by Webster, the chlorofluorination step produces a number of saturated perhalogenated chloronuorocarbons, including: (A) C3CI5F3; (B) C3CI4F4; (C) C3CI3F5; (D) 1,2-dichlorohexafluoropropane (CF3-CCIF-CCIF2, CFC-216ba); (E) 2,2-dichlorohexafluoropropane (CF3-CC1:-CF3, CFC-2I6aa); (F) i- Replacement sheet 1, Under Article 34 chloroheptafluoropropane (CF3CF2CCIF2, CFC-217ca); (G) 2-chloroheptafluoropropane (CF3CCIFCF3, CFC-217ba); and (H) octafluoropropane (CF3-CF2-CF3, FC-218). While the FC-218 is useful and can be separated from other perhalogenated reaction products, it is not an efficient or economical intermediate in the synthesis of HFC-227ea, HFC-227ca or FC-1216. As indicated in the "491 patent, the predominant reaction products resulting from the chlorofluorination of propane with HF and CI2 is CFC-216aa, which is fluorinated and then dehalogenated to hexafluoropropene (FC-1216). Due primarily to environmental as well as toxicological concerns, demand is increasing for isomerically pure chlorofluorocarbons and hydrofluorocarbons. Teachings such as those described above cannot begin to address these issues and concerns because efficiency of production as well as isomeric purity were not contemplated. Prior art of similar chemistry does not allow for the exclusive production of the HFC-227ea, but only as a mixture or by-product with FC-1216. The unsuitability of FC-1216 for a fire suppressant does not make this a viable or efficient route. A need exists to develop a method of chlorofluorinating inexpensive C-3 reactants that eliminates one or more by products of chlorofluorination, particularly FC-218 and undesired isomers which cannot be recycled to produce HFC-227ea or HFC-227ca. Moreover, a long felt need exists for extending the lifetime of catalysts used in these reactions. Furthermore, the reaction products generated from these steps require purification. U.S. Patents 6,018,083 to Manogue and 6,211,135 to Miller respectively teach the partial separation (azeotropes) of chlorofluorocarbons C3CIF7 (CFC-217) and C3CI2F6 (CFC-216) from HF. These references demonstrate the practical difficulty of separating reaction product mixtures with conventional distillation techniques. The formation of azeotropes requires the use of subsequent or expensive distillation techniques to produce a pure product that can be used as a final product or as an intermediate reactant. A need remains for processes that separate chlorofluorination reaction products without forming azeotropes. The present invention provides processes for the chlorofluorination of aliphatic, olefinic or partially halogenated hydrocarbons in the presence of a catalyst that results in the substantial elimination of FC-218 as a by-product in the chlorofluorination reaction and that efficiently converts the starting material to the desired isomer. The present invention also provides processes for the efficient purification of reaction product streams. One embodiment of the present invention is directed to a process for the manufacture of HFC-227ea, including a novel and highly selective method of preparing a CFC-2I6aa intermediate by chlorofiuorinating C-3 reactants with HF and CI2 without the formation of substantial or even detectable amounts of FC-218 or undesired isomers. In accordance with the present invention, the C-3 reactants are chlorofluorinated in a first step with hydrogen fluoride and chlorine in the presence of a metal containing catalyst at a first temperature. The reaction products from this first step are then fluorinated with hydrogen fluoride at a second temperature resulting in an unexpectedly high yield of CFC-216aa without the formation of FC-218. -• One aspect of the present invention is to provide a method of manufacturing a CFC-216aa intermediate by chlorofluorination of C-3 reactants such as aliphatic, olefinic or partially halogenated hydrocarbons having at least three carbon atoms, wherein the process provides new and unexpected selectivity for the CFC-216aa reaction product. Another aspect of the present invention provides a method of manufacturing a CFC-216aa intermediate for preparing CFC-217ba and subsequently preparing HFC-227ea with excellent selectivity and yield, without the formation of FC-218 or undesired isomers. Another embodiment of the present invention includes a process step for hydrodehalogenating CFC-217ba to produce HFC-227ea by contacting CFC-217ba with H2 in the presence of a metal containing catalyst. According to another embodiment of the present invention, the hydrodehalogenation step is provided as just described, with the addition of water to prolong catalyst life. The present invention also provides a process for separating the isomers HFC-227ea and HFC-227ca by combining the isomeric mixture with a chlorofluorocarbon and subsequently separating the mixture by distillation. In one embodiment the chlorofluorocarbon is CFC-217ba. Another process according to the present invention provides for the purification of halogenation reaction products into HF and chlorofluorocarbons. In a more specific embodiment, the halogenation reaction product includes CFC-216aa. Still another process for separating halogenation reaction products is provided wherein the reaction products are combined with water and cooled to a sufficient temperature to form a gas phase and top and bottom liquid phases. According to one embodiment, the gas phase contains primarily C-3 chlorofluorina".ed compounds having at least six fluonne atoms, the top liquid phase is primanly an aqueous liquid phase and the bottom liquid phase contains C-3 chlorofluorinated compounds having less than six iTuorine atoms. An additional process according to this invention provides for separating C-3 chlorofluorinated compounds from a halogenation reaction product. One embodiment of this invention includes the adjustment of a halogenation reaction product to a sufficient temperature to separate the reaction product into three phases: an upper gas phase and top and bottom liquid phases, wherein the upper gas phase contains pnmarily HCl, the top liquid phase contains HF and the bottom liquid phase contains essentially acid-free C-3 chlorofluonnated compounds. In still another process of the present invention methods are provided for synthetically increasing the isomeric purity of a mixture. AccordINg to one embodiment, an isomeric mixture of C-3 chlorofluorinated compound isomers is heated in the presence of a catalyst to a sufficient temperature to increase the isomeric purity. In a more specific embodiment, the C-3 chlorofluonnated compound isomers are CFC-2I7ba and CFC-217ca. In still another embodiment of the present invention a process is provided for selectively halogenating isomers within an isomeric mixture. In a particular embodiment, the isomeric mixture is exposed to Cb in the presence of a catahst at a sufficient temperature to halogenate at least one isomer. Preferably the isomeric mixture includes the isomers HFC-227ea and HFC-227ca. The above and other embodiments, aspects, alternatives and advantages of the present invention will become more apparent from the following detailed description of the present invention taken in conjunction with the drawings. Replacement sheet 5, Under Article 34 DESCRIPTION OF THE FIGURES Figure 1 is a schematic representation of one embodiment of the present invention. Figure 2 is a graphical representation of the isotherms observed during the processes of the present invention. Figure 3 is a block diagram of an embodiment of the present invention. Figure 4 is a block diagram of an embodiment of the present invention. Figure 5 is a block diagram of an embodiment of the present invention. Figure 6 is a block diagram of an embodiment of the present invention. Figure 7 is a graphical representation of catalyst life observed according to an embodiment of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to Fig. 1, in one embodiment this invention provides processes for the production of chiorofluoropropanes and fluoropropanes from aliphatic, olefinic, or partially halogenated hydrocarbons having at least three carbon atoms. Other embodiments of this invention provide specific processes for hydrodehalogenation, as well as, isomer and reaction product purification. Selected embodiments of this invention will be descnbed in turn beginning with the broad chemical process steps used to produce selected chlorofluorocarbons and fluorocarbons. In part, this invention stems from the discovery that the majority of the isomer in the final chlorofluorocarbon or hydrofluorocarbon product originates as an undesired isomer which forms in the initial reactions. This isomer and its downstream counterparts are passed to subsequent reactions undergoing the same chemical transformation as the desired isomeric material. Fortunately, CFC-216ba and its downstream counterparts, have different reaction profiles allowing for their reduction with each subsequent step. Unlike CFC-217ca and HFC-227ca. CFC-2l6ba is not a "dead end" isomer. A majority of this material is directly converted to the desired isomer CFC-2I7ba in subsequent steps performed in accordance with the present invention. Without being confined to any theory, the formation of the undesired isomer takes place in these early reactions by the premature fluorination of the geminal C-2 carbon of aliphatic, olefinic, or partially halogenated hydrocarbons having at least three.carbon atoms. The production of CFC-2l6ba is but just one example of this type of chemistry. Referring now to Fig. 2, formation of excess amounts of CFC-216ba during halogenation has been obser\ed when the reaction is allowed to exotherm excessively. The large amounts of energy released during this exotherm are probably the ultimate reason for excess CFC-2i6ba isomer formation. When these types of conditions are allowed to prevail, ratios as low as 2:1 CFC-216aa:CFC-216ba can be observed in these early reaction streams. One way to control this phenomenon can be to carefully operate the initial halogenations so as to avoid uncontrolled exotherms. The reactor used according to the present invention has the ability to use cool heat transfer oil and includes conventional chemical and engineering controls to insure suppression of exotherms. In another aspect of the present invention. HP can be replaced as the main diluent for the reaction. Figs. 3-4 show a schematic flow diagram for a process according to the present invention that includes a two temperature zone chlorofluorination of a C-3 reactant selected from propane, propylene, partially halogenated C-3 acyclic hydrocarbons, and mixtures thereof, with hydrogen fluoride and chlorine in the presence of a chlorofluorination catalyst. The process is highly selective in the production of CFC-216aa, without the formation of any significant amount of FC-21S (0 to less than 0.5 percent by weight). The high yield and selectivity of the process of the present invention in the synthesis of CFC-216aa is very advantageous for the subsequent production of HFC-227ea as discussed below. The present invention provides, in one aspect, two step processes for efficiently producing CFC-216aa. The chemical steps can include the sequential replacement of hydrogen with chlorine and the subsequent partial replacement of chlorine with fluorine atoms. Multiple products m.ay be formed with intermediate fluorinated materials being the majority. Careful temperature control may minimize by-product formation. Typical reaction products may include C-3 molecules with 2 to 7 fluorine atoms, the rest being chlorine. The cracking of the C-3 backbone to form C-1 and C-2 materials as undesired impurities has also been observed. According to one embodiment, the output of this reactor can be fed directly into a subsequent reactor as shown in Fig. 4, which is run at a higher temperature. Individual reactants may be fed under flow control to vaporizer(s) 14. as shown in Fig. 3. The vaporized chlorine and HF are mixed and fed into a superheater. It has been determiined that careful mixing of the reactants and temperature regulation may help to control reaction exotherms and lack of control may lead to the formation of undesired by-products arising from cracking the C-3 backbone. may be summarized, as follows, with high selectivity in the production of CFC-216aa: CH3CH2CH3, CH3CH=CH2 and/or C3HvXz+HF+Cl2^CFC-216aa+HCl (X=halogen; y=0-8, z=8-y; or y=0-6, z=6-y) According to one aspect, the process includes a first step, wherein C-3 reactants selected from the group consisting of aliphatic, olefinic or partially halogenated hydrocarbons having at least three carbon atoms are contacted with CI2 and HF in the presence of a metal containing catalyst. As illustrated in Fig. 3, this reaction is preferably performed in the gas phase by the careful mixing of C-3 reactants with a mi.\ture of hydrogen fluoride (HF) and chlorine (CI2) in the presence of a metal containing catalyst at a sufficient temperature to form perhalogenated compounds. In one embodiment of the present invention, the C-3 reactant is selected from the group consisting of aliphatic, olefinic and/or partially halogenated hydrocarbons. The C-3 reactant may be premised with hydrogen fluonde, and then mixed with chlonne before entering chlorofluorination reactor 16 containing a fixed bed of metal containing catalyst. Aliphatic hydrocarbons having at least three carbon atoms are known to those skilled in the art to be alkanes, hydrocarbons characterized by a straight or branched carbon chain. These types of compounds include propane. Olefinic hydrocarbons having at least three carbon atoms are known to those having ordinary skill in the art to be unsaturated aliphatic hydrocarbons having at least one double bond. These types of compounds include propene. Partially halogenated hydrocarbons having at least three carbon atoms are known to those having ordinary skill in the art as aliphatic or olefinic hydrocarbons wherein one or more hydrogens have been replaced by halogens. According to one emibodiment of the present invention, the HF and C-3 reactants are premixed before being combined with the chlorine gas and conveyed into a chlorofluorination reactor. It is preferred to premix (dilute) the C-3 reactant with the hydrogen fluoride reactant prior to combining the HF/C-3 gas reactants with the chlorine gas reactant in order to minimize the potential reaction of the C-3 reactant, e.g., propane and/or propylene with concentrated chlorine gas. Accordingly, at least one of the C-3 reactant or the chlorine, preferably both the C-3 reactant and chlorine, may be diluted with hydrogen fluoride prior to combining the C-3 reactant with the chlorine gas. In one embodiment of the present invention the HF is anhydrous. It has been determined that recycled or reagent grade HF may used. The type of HF used to perform this aspect of the invention is not critical and specific types and qualities will be recognized by those skilled in the art. The CI2 likewise is a matter of choice to those having skill in the art. In one embodiment, technical or pure-grade anhydrous CU is utilized. The halogenation of aliphatic, olefinic, or partially halogenated hydrocarbons having at least three carbon atoms is a highly exothermic reaction which may be controlled through the use of excess quantities of hydrogen fluoride, a diluent, or an external heat transfer medium together or in combination, to absorb the heat evolved and to maintain temperature control of the mixture. To reduce the impact of exotherms, preferably, a stoichiometric excess of hydrogen fluoride may be maintained in order to minimize decomposition of the C-3 reactant to C-1 and C-2 by-products, and the formation of the less desired CFC-216ba. Preferably, about 6 to about 64 moles of HF per mole of C-3 reactant may be utilized. It is preferred to provide an excess of chlonne gas as well, preferably about 8 to about 10 moles of CI; per mole of C-3 reactant. However, an excess of CI2 is not required. In a preferred embodiment, the ratio of CI; to C-3 reactants can be about 8.2:1. The molar ratio of HF to CI2 maybe from about 0.75:1 to about 8:1. Preferably, the molar ratio of H to CI; maybe about 4:1. Moreover, in another embodiment, a diluent may be added to the reaction to decrease undesired isomer and formation of cracking materials. Preferably, the chlorofluorination reactor 16 used to perform this invention may be maintained at a reaction pressure of about 0 psig to about 750 psig, preferably about 0 psig to about 750 psig and at a temperature in the range of about 150°C to about 450""C, and preferably about 220"^C. Residence time in chlorofluorination reactor 16 may be in the range of about 0.5 seconds to about 30 seconds and preferably about 5 to about 10 seconds. An exemplary reaction mixture exiting Step I shown in Fig. 3 is rich in C3C!iF4 and C3CI3F5, but may also contain CFC-216aa and many other under fluonnated compounds. In an exemplary aspect, reaction products of this first step are conveyed directly to Step 11, as shown in Fig. 4. However, it is recognized that the reaction products of Step I, as shown in Fig. 3, may be further purified or supplemented prior to continuing on to Step II. A main goal in Step II can be the selective fluorination of under-fluorinated compounds to the desired isomer CFC-216aa. In the illustrated embodiment, the second step in this process may replace all of the terminal chlorine substituents with fluorine to produce CFC-2l6aa. According to one aspect of the present invention, this is accomplished through the use of one or more of high temperature reaction conditions, excess HP. and a metal containing catalyst. As shown in Fig. 4. the Step I reaction stream is directly fed into a superheater 24. Optimally, this stream is then fed to Step II reactor 26. Again, as before in Step I, careful temperature regulation can be used to control the reaction. The second reaction can take place either in the same reactor as exemplary Step I or, preferably, in a second reactor. The second reaction can be carried out at a higher temperature than the first reaction with a stoichiometric excess of hydrogen fluoride. .A.ccording to one embodiment, a stoichiometric excess of chlorine can be used to ensure chlorofluorination of the first reaction products. Reactor 26 can be a fixed-bed reactor ha\ ing a metal containing catalyst, maintained at a reaction pressure of about 0 psig to about 750 psig and preferably about 100 psig, and at a temperature higher than the temperature required in exemplary Step I. Step II may occur at a temperature ranging from about 300°C to about 550°C, and preferably at about 470~C. It is preferred that the molar ratio of reactants in Step 11, should be maintained at about 6 to about 64 moles of hydrogen fluonde per mole of perhalogenated compounds. As in Step I, the source and quality of anhydrous HF used in Step n is not critical. It is to be understood by those skilled in the art that anhydrous, recycled, and/or differing grades of HF can be used in Step 11. As in Step I, a diluent may be added to control exotherms and increase isomeric vield. The metal containing catalyst used in Step I or Step II can be any known catalyst useful for reacting C-3 reactants or perhalogenated compounds with HF and/or CI2, including those described in U.S. Patent Nos. 5,177,273 and 5,057,634 to Webster, hereby incorporated by reference. These catalysts include catalysts consisting essentially of chromium; catalysts consisting essentially of chromium oxide in combination with a support (e.g. refractory oxide); catalysts consisting essentially of chromium oxide modified with up to about 10 percent by weight based upon the weight of chromium in the catalyst of metal selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, other metals and mixtures thereof; and catalysts consisting essentially of chromium oxide in combination with the refractory oxide and modified with up to about 10 percent by weight based upon the weight of chromium in the catalyst of metal selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, other metals and mixtures thereof. Chromium oxide catalysts and their preparation in the art of perhalogenation are well known. The chromium oxide and metal modified chromium oxide catalysts may be unsupported or supported. Catalysts consisting essentially of either chromium oxide or metal modified chromium oxide in combination with a support (e.g., alumina) may be prepared by conventional procedures (e.g., impregnation of the support using a suitable soluble chromium salt alone or in combination with a suitable soluble salt of the metal modifier). In addition, catalysts of this invention can also be prepared by co-precipitation methods, which are known in the art. Typically for refractory oxide containing catalysts, the refractory oxide constitutes from about 80 to 99.5 weight percent of the catalyst. Catalysts consisting essentially of fluorinated chromium oxide, or fluorinated chromium oxide in combination with a refractory oxide, or fluorinated metal modified chromium oxide or fluorinated metal modified chromium oxide in combination with a refractory oxide may also be used. Indeed, the catalysts are preferably fluorinated prior to use for the halogenation process of this invention by treatment with a suitable fluorine-containing compound (e.g., HF, SF4, CCI3F, CCI2F2, CHF3, or CCI2F-CCIF2) at elevated temperatures. Pretreatment of catalysts containing refractory oxides such as alumina are considered particulariy useful. Such treatments are well known to the art. The treatment with HF or other fluorine-containing compound can conveniently be done in the same reactor which is to be used for the production of the selected halohydrocarbon product(s). Iron and nickel containing catalysts, specifically iron chloride and nickel chloride catalysts, supported or unsupported may be employed as well. The catalysts of this invention can undergo changes in composition and/or structure during use. One skilled in the art will recognize, for example, that during use the catalyst may be in the form of an oxyfluoride, an oxychloride, an oxychlorofluoride and/or an oxide, and/or may have a different crystalline structure from the catalyst charged to the reactor. Charging the reactor with these compounds (e.g., an oxyfluoride, etc.) or with any compound(s) convertible to these compounds under reaction conditions is considered an equivalent procedure \vi:hin the scope of this invention. In this and the other reaction sequences, reaction with HP includes either high temperature vapor phase reaction or lower temperature reaction in the presence of a liquid phase catalyst such as SbCls/HF or SbF5- the vapor phase process is preferred. Two metal containing catalysts that have been found to be paricularly useful for the chlorofluorination reactions include: (1) FeCls on a suppon, particularly active carbon, that is dr.ed and then tluorinated, e.g., with HF, preferably an HF/NT mi.xture. with or without O:, at about 200°C to about 270°C and then treated with HF, with or without O2 or Ch activation, within the range of about 270°C to about 320°C. It is preferred that the percent by weight of FeCI;, in the metal containing catalyst be in the range of about 2% to about 36^f by weight on a catalyst support, which is preferably activated carbon, preferably at about 5~c to about 10% by weight FeCls. It is useful to fluonnate the metal containing catalyst for a period of at least about 2 hours, preferably about 2 to about 16 hours, more preferably about 8 hours, gradually increasing the temperature within the rage of from about 200°C to at least the chlorofluorination reaction temperature, e.g., up to about 320°C; ar.d (2) CrCb, particularly chromium chloride hexahydrate (CrCl;, • 6H2O) on a support, particularly active carbon, that is dried and then fluorinated. e.g., with hydrogen fluoride gas (HF), in the samie manner as fluorination of the FeCl;, catalyst with or without O2 or CI2 activation. Non-limiting e.xamples 1, 2 and 3 demonstrate the preparation of catalysts suited for the present invention and non-limiting example 4 demonstrates the activation of catalyst suited for this invention. Generally, all fluorination catalyst can be prepared by mixing appropnate amounts of the selected metal salt and support (if necessary) in DI Water. This mixture may be allowed to stand for approxim.ately 0.5 hour and the excess water can be filtered off by vacuum filtration. The resulting solid may then be dried overnight in a gravity oven at 115°C and then charged to the reaction tubes where it can be further dried at I50°C with a inert gas purge and then activated with HF before the reaction feeds are started. Example 1: FeCl-j/Activated Carbon Catalvst Preparation: Iron (III) chloride hexahydrate (20 grams) was dissolved in deionized water (300 cc). The solution was then mixed into and absorbed by 200 grams of active carbon pellets and air-dried overnight. Example 2: CrClVActivated Carbon Catalvst Preparation: Chromium (III) chloride hexahydrate (12.6 grams) was dissolved in deionized water (100 cc). The solution was mixed into and absorbed by 75 grams of active carbon pellets and air-dried overnight. Example 3: NiCl;;/Activated Carbon Catalvst Preparation: Nickel (II) chloride hexahydrate (13.8 grams) was dissolved in deionized water (100 cc). The solution was mixed into and absorbed by 75 grams of active carbon pellets and air-dried overnight. Example 4: Metal Chloride/Carbon Catalvst Activation Methods: The chJorofluorination catalyst was activated using a chlorofluorination reactor with HF. The following description gives the detailed procedures for three methods of chlorofluorination catalyst activation. (a) The FeCb/carbon catalyst of Example 1 was added to both Step I and Step II reactors and the catalyst in each reactor was dried with N2 and fluorinated with HF/N2 to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF mole of active metal in the catalyst at 250°C for 9 hours. The metal containing catalyst in the Step I reactor was then further activated with HF/N2 to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF per mole of active metal in the catalyst at 285°C for another 14 hours. The metal containing catalyst in the Step II reactor was then funher activated with HF\N2 to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF per mole of active metal in the catalyst at 465°C for another 14 hours. (b) The same procedure discussed above in method (a) was performed for drying metal containing catalyst with N2 and fluorination with HF/N2. The metal containing catalyst was further activated with 2% by weight O2 along with HF/N2 to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF per mole of active metal in the catalyst for 12 hours, then another 2 hours without O2. (c) The same procedure was performed for the catalyst activation as described above in method (b) except using 2% by weight CI2 instead of 2% by weight O2. For all reactions exemplified herein, except where noted, two 41.6 cc, 12.7 mm (OD), Incone® reactor tubes heated with ceramic fiber, radiant heat electric ovens were utilized as reactors. The tubes were utilized alone or in tandem to perform the reaction examples. Non-limiting example 5 demonstrates the results of chiorofluorination, according to the present invention. Example 5: Chiorofluorination of C-3 Reactants: Step I was conducted according to the parameters indicated in Table 1 below. The reaction products of Step I were conveyed to the Step II reactor. The Step II reaction was also conducted according to the parameters indicated in Table 1. Like Step I, Step II was performed with a fixed-bed reactor containing a metal containing catalyst. The specific types of catalyst are described in Table 1 below. The hydrogen fluoride used in Step I and Step II was anhydrous liquid HF that was vaporized to provide anhydrous HF gas. The results of the present example are shown below in Table 1. As demonstrated in Table 1 above, iron and chromium chloride catalysts are particularly well suited for use as metal containing catalysts according to the present invention. In particular, when utilizing the iron catalyst no detectable levels of the undesired CFC-216ba isomer were found. Non-iimiting example 6 demonstrates the reaction efficiency of the present invention. Example 6: Mass Balance Demonstration: Step I was conducted at a temperature of about 280°C with a molar ratio of HF:Cl2:C-3 reactant, 6:9:1. Residence time in the Step I reactor was about 10 t seconds. The reaction products of Step I were conveyed to the Step II reactor. The Step II reaction was carried out at about 465°C. Like Step I, Step II was performed with a fixed-bed reactor. The chlorofluorination catalyst used in both halogenation reactors (Step I and Step II) was a supported chromium containing catalyst. The reaction products, contained predominantly CFC-216aa, hydrogen fluoride and hydrogen chloride gas, and were conveyed into a central portion of a strip column for HCl removal. The chlorofiuorination reaction products were collected for analysis by gas chromatography. The amount of the specific compound is indicated in terms of chromatographic area percent. For this, and the following examples, area percent is consistently utilized to demonstrate the advantages of the present invention. The reaction products were collected for analysis and reported in Table 2 below. As Table 2 shows, (mass balance) of the present invention is good at approximately 95% recovery of reactants. Non-limiting example 7 demonstrates the flexibility of starting material selection of the present invention. Example 7: Use of Varying Starting Materials and Reagent Proportions: Tandem Incone® pipes were charged with supported chromium oxide catalyst. Liquid HF was vaporized and the HF vapor was then mixed with propylene/propane gas through an in-line static mixer and then mixed with Cb at the top of the Step I pipe, according to the parameters shown below in Table 3. The reaction products from the Step I pipe were conveyed to the Step II pipe and the Step II reaction products were fed into a strip column to separate HCl, CI: and light components from HF, CFC-216aa and heavy components that were removed from the bottom of the strip column. The strip column bottom components were then fed into a phase separator to separate HF from organic materials, including C3CI2F6 for analysis by gas chromatography. Recovered or recycle HF was fed back to the Step I pipe vaporizer. The underfluorinated organic materials were collected and recycled back to the Step I pipe for further fluorination. The results of using propane or propene as a C-3 reactant is shown below in Table 3, propene (C3H6, Runs A and B) or propane (CsHg, Runs C and D) as the raw material (C-3 reactant) for the present invention. The results of using varying proportions of reactants and the effects of additions of a diluent are shown below in Table 4. The exotherms observed during run conditions dictated in Table 4 are demonstrated in Figure 2. In non-limiting example 8 below, the benefit of combining reagents in a specified order according to the present invention is demonstrated. Example 8: Raw Material Mixing Effect: Two tests were performed by: (1) using a static mixer to first mix HF with C3H8 and then mix the HF/CjHj mixture and Ch in another mixer before the Step I reactor; and (2) first mixing the HF with CI2 using a static mixer, and then adding the HF/CI2 mixture to C3H8 in another mixer before the Step I reactor. The reaction parameters and results of this example are listed in Table 5 below. As Table 5 demonstrates, the combination of reactants plays no role in the overall selectivity of C3C2F6. Even though it appears conversion is increased it is probably due to increased residence time in the reactor, rather than order of mixing of reactants. Another process according to the present invention provides for purifying halogenation reaction products. For purposes of the present invention, halogenation reaction products encompass those reaction products as described above and refers to reaction products of reactions wherein chlorine and/or fluorine atoms replace hydrogen or halogen atoms along carbon atom backbones. In most cases the products of these reactions include HE and organic chlorofluorinated compounds. In another embodiment of the present invention the C-3 chlorofluorinated compounds have at least six fluorine atoms. Referring to Fig. 4, according to one embodiment of the present invention to separate HF from C-3 chlorofluorinated compound reaction products, the temperature of the chlorofluorination reaction product is reduced to a sufficient point within phase separator 28 to separate the reaction products into separate top and bottom liquid phases. According to one embodiment, the temperatire used to accomplish this separation is from about -30°C to about -10°C. In a preferred embodiment the temperature is about •20°C. To complete the separation of the HF from the C-3 chlorofluorinated compounds (which can have at least six fluorine atoms) the top phase (formed by lowering the temperature of the chlorofluorination reaction products) is removed to obtain essentially organic free HF and/or simultaneously the bottom phase is removed to obtain essentially acid free C-3 chlorofluorinated compounds. This separation can be performed on an industrial scale continuously in a unit operation or in a batch operation. Persons skilled in the chemical engineering arts will routinely be able to select the type of apparatus necessary to perform this liquid/liquid phase separation. One of the distinct advantages of this process for separation HF from C-3 chlorofluorinated compounds is that expensive distillation is not required. Nor is there a production of the HF/C-3 chlorofluorinated compound azeotrope. Problems associated with distillation processes and the production of HF/chlorofluorocarbon azeotropes are discussed in U.S. 6,211,135 to Miller, herein incorporated by reference. Referring now to Figure 4., it has been found during the course of the present invention that at low temperatures, the HF phase 30 is virtually free of organic C-3 chlorofluorinated compounds and likewise the organic phase 32 having C-3 chlorofluorinated compounds are virtually free of HF. Moreover, because the separation according to the present invention results in two product streams, either product may without further purification be sent on to additional reaction steps or returned or recycled to previous reaction steps. Because the phase separation of the present invention is performed in the liquid phase, any pressure sufficient to maintain the materials in the liquid phase can be used according to the present invention. Preferred embodiments of the present invention use low temperatures and ambient pressures. However, the resulting nonazeotropic mixtures of HF and organic C-3 chlorofluorinated compounds exist at different temperatures depending on the pressure of the system. The present invention providing for HF/organic separation is demonstrated below by non-limiting example 9. Example 9: HF/Organic Phase Separation: A chlorofluorination reaction product including HF, CI2 and CFC-216aa was purified according to the present invention. The reaction feed stream included 0.04 kg/s CI2, 0.003 kg/s propane, 0.006 kg/s HF and 0.084 kg/s recycled HF with a reaction product stream containing 75 weight percent CFC-216aa on an acid free basis. The HCl was removed by distillation and the bottoms of the distillation column (HF and organic chlorofluorination reaction products) was cooled and sent to a 757 liter liquid phase separation tank where it was chilled. The vapor pressure of the mixture in the phase separator was 1.97 Pa at 21.8°C. The mixture separated into two phases, a bottom phase and a top phase. The bottom phase comprised a liquid organic phase that was decanted off and scrubbed and purified to produce pure CFC-216aa. The top phase comprised a liquid HF phase that was decanted off and recycled to a previous reaction step. The organic phase was analyzed and the results are represented in Tables 6 and 7 below. As this example demonstrates the organic phase, once separated according to an mbodiment of the present invention, is essentially acid-free. This allows for the mmediate isolation of specific chlorofluorination reaction products without the need for ostly and inefficient distillation. Moreover, Table 7 demonstrates that other halogenated rganics can be separated from HF, according to the present invention. These chlorofluorination reaction products can be isolated according to another process of the present invention as herein described next. Another process according to the present invention is the separation of the C-3 chlorofluorinated compounds having at least six fluonne atoms from C-3 chlorofluorinated compounds having less than six fluorine atoms. This separation process is extremely useful in order to maintain the compound purity of chlorofluorinated compounds sought to be produced. According to one embodiment of the present process, a solution comprising C-3 chlorofluorinated compounds having at least six fluorine atoms and C-3 chlorofluorinated compounds having less than six fluorine atoms is provided. This solution is derived from a reaction product or a refined reaction product of a chlorofluorination reaction or the phase separation or distillation product after a chlorofluorinated reaction. In one embodiment of the present invention the C-3 chlorofluorinated compounds having at least six fluorine atoms comprises CFC-216aa. However, this invention is not limited to the source of this mixture. According to the present invention, the solution is contacted with the water to form a mixture of organics and water. This may be performed using various blending or mixing apparatuses, the particular type of apparatus is not critical and those skilled in the art will recognize apparatus suited for preparing this mixture. It is preferred that deionized water be added to the solution to obtain the mixture. However, other forms of water can be used having various salt concentrations and/or pH levels. According to another embodiment, the water mixed with the solution comprising the chlorofluorinated compounds may include a basic compound, such as potassium hydroxide. Persons having skill in the art will understand that a compound that is basic is a compound that is more alkaline than other compounds. These are known to those skilled in the art as compounds that when added to water raise the pH of the water from its neutral pH to a higher than neutral pH. According to one embodiment of the present invention, after mixing, the temperature of this water mixture is then adjusted to a sufficient temperature to separate the water mixture into at least three phases, including an upper gas phase containing C-3 chlorofluorinated compounds having at least six fluorine atoms, a top aqueous phase, and a lower liquid phase containing C-3 chlorofluorinated compounds having less than six fluorine atoms. The temperature sufficient to obtain the three distinct phases described above is from about 25"C to about 75°C. The preferred temperature used to obtain these three phases is about 50°C. The above process of separating the C-3 chlorofluorinated compounds alleviates the need for cost intensive and inefficient distillation. The separation of the C-3 chlorofluorinated compounds can be performed as a continuous phase separation process or as a batch phase separation process, applying techniques known to those having skill in the art of phase separation. The upper gaseous phase can be removed to obtain essentially pure C-3 chlorofluorinated compounds having at least six fluorine atoms while at the same time or, alternatively in a batch process, the bottom liquid phase containing C-3 chlorofluorinated compounds having less than six fluorine atoms can be removed either leaving behind or allowing for the removal of the top aqueous phase. Upon removal, these phases can be ftirther processed or retained as end products. According to one embodiment of the present invention, the chlorofluorinated compounds having at least six fluorine atoms are conveyed to an additional reaction step to increase the number of fluorine atoms present. Example 10: Separation of Fluorinated Compounds: The containers of crude C3CI2F6 from vanous production runs of Steps I and II contained C3CI2F6 and numerous other unidentified underfluorinated compounds, and possible small amounts of H;0, HF, Cb, and HCl. Approximately 73 kg of crude CsCNFo were fed from a heated cylinder to a 57 liter Halar® lined scrubber tank. The scrubber tank contained a level gauge and an external heat tracing with a skin temperature thermocouple. The feed line into the tank was through a dip tube. The tank was initially filled with a 5% KOH/water solution and the temperature of the tank was heated to 50°C. The mixture separated into three phases: an upper, primarily gaseous phase; a top liquid, primarily aqueous phase; and a bottom primarily organic phase. The top gas phase was removed as a vapor stream and fed to a Halar lined scrubber. The vent gas was open to a molecular sieve dryer bed which fed into a chilled collection cylinder on a scale. Upon completion of the scrubbing of the C3CI2F6, the underfluorinated organics collected from the bottom phase was approximately 9.1 kg of material. The primary components of this organic liquid were C3CI4F4, and C3CI3F3 and C3CI2F6. As table 8 demonstrates, underfluorinated compounds can be efficiently separated from C3CI2F6 according to the present invention. As shown in Fig. 5, the present invention provides a third reaction step (Step III) for the selective fluorination of C3CI2F6 to CFC-217ba. The predominant reaction occurring in this step is as follows:C3Cl2F6 + HF -^ CF3-CFCI-CF3 + HCl Preferably. Step III proceeds in the gas phase with excess anhydrous HF over a metal containing catalyst. According to one embodiment of the present invention. the reactants of Step III are fed under flow control to vaporizer(s) 34. These vaporized reactants include CFC-216aa which are fed to reactor 36. In Step III isomer formation can be controlled by selective fluorination. Since the undesired CFC-216ba contains 2 chlorine atoms it is not technically a "dead end" material. It has been demonstrated that by selective fluorination CFC-216ba will lead to CFC-217ba but CFC-216aa does not readily convert to CFC-217ca. Isomer formation is also effected by conversion. According to one embodiment, the high yield CFC-2I6aa chlorofluorination product recovered from Step II reaction described previously is mixed with hydrogen fluoride and contacted with a metal containing catalyst. Residence time of Step III is in the range of about two seconds to about 60 seconds, and preferably about 20 seconds to about 30 seconds. Referring to Figure 5, according to one embodiment, reactor 36 is a fixed bed reactor having a metal containing catalyst on a suitable solid support. The metal containing catalyst can be any catalyst known as being useful for the fluorination of C-3 chlorinated hydrocarbons with hydrogen fluoride. Preferred catalysts for the synthesis of CFC-217ba are supported metal containing catalysts. Metals such as iron, zinc, chromium and mixtures thereof are particularly useful as catalysts for the conversion of C3CI2F6 to CFC-217ba. Acceptable results can be obtained vrith other metal-containing catalysts, provided the temperature, contact time, and other reaction conditions are suitably selected. Suitable catalysts are supported catalysts that are dried and HF/N2 treated at 250°C, e.g., for 9 hours, and then HF/N2 treated at 465°C, e.g., for another 14 hours using a stoichiometric excess of HF, e.g., about 1.5-3 moles of HF per mole of active metal in the catalyst. This catalyst activation process can include O2 or CI2 gas at a concentration of about 0.5% to about 5% by weight, e.g., 2%. The catalysts are particularly effective when activated according to one of the following three methods (a), (b), or (c) described below: (a) The catalyst is dried with N2, fluorinated with HF/N2 at 250°C for 9 hours. The catalyst is then further activated with HF/N2 at 465°C for another 14 hours. (b) The same procedure is performed for catalyst drying and fluorination as described above in method (a). The catalyst is then further activated with 2% by weight O2 along with HF/N2 for 12 hours, then another 2 hours without O2. (c) The same procedure for the catalyst activation as described above in method (b) is used except using 2% by weight Clj instead of 0:. Non-limiting examples 11 and 12 demonstrate the preparation of catalysts suited for the present invention and non-limiting example 13 demonstrates the activation of catalyst suited for this invention. Example 11: FeCh/Activated Carbon Catalvst: Iron (III) chloride hexahydrate (3.78) moles was dissolved in deionized water (1000 cc). The solution was mixed into and absorbed by 1000 grams of active carbon pellets and air-dried overnight. Example 12: CrCla/Activated Carbon Catalvst: Chromium (III) chloride hexahydrate (5.14 moles) was dissolved in deionized water (2100 cc). The solution was mixed into and absorbed by 3000 grams of active carbon pellets and air-dried overnight. Example 13: Metal Chloride/Carbon Catalvst Activation Methods: The catalyst was activated using a fluorination reactor with HF. The following description gives the detailed procedures for three methods of fluorination catalyst activation. (a) The FeCb/carbon catalyst of Example 11 was added to Step III reactor (herein, the reactor is identical to those reactors described previously) and the catalyst was dried with N2 and fluorinated with HF/Ni to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF per mole of active metal in the catalyst at 250°C for 9 hours. The catalyst was then further activated with HF/N2 to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF per mole of active metal in the catalyst at 465°C for another 14 hours. I (b) The same procedure discussed above in method (a) was performed for metal containing catalyst drying with N2 and fluorination with HF/N2. The metal containing catalyst was further activated with 2% by weight O2 along with HF/N2 to provide a stoichiometric excess of HF in the range of about 1.5 to about 3 moles of HF per mole of active metal in the catalyst for 12 hours, then another 2 hours without O2. (c) The same procedure was performed for the catalyst activation as described above in method (b) except using 2% by weight CI2 instead of 2% by weight O2. The HF:C-3 reactant molar ratio utilized in Step III is preferably in the range of about 1-30 moles of HF per mole of C-3 reactants and the reaction pressure is in the range of about 1-53 Pa, and preferably about 8 Pa at a temperature of about 200°C to about 550°C, and preferably about 485""C. Like Steps I and II previous, Step III may combine a diluent with the reactants. By way of non-limiting example 14, a reaction according to an embodiment of the present invention is shown below. Example 14: STEP III fC^ChF^ ^ CFC-2l7ha): A 51 mm I.D. x 1.3 m long Incone-® pipe reactor was heated to 485°C by an electric heater. The reactor was connected to a distillation column, which had a pressure control valve to maintain the system pressure at 5 Pa. The reactor was charged with a supported chromium oxide catalyst. 13.88 g/min HF and 6.05 g/min CFC-216aa were fed into a vaporizer. The gas mixture was conveyed to the reactor, and products were removed and fed into a distillation column to separate HCl, CFC-217ba and light components. It is to be understood that the Step III reaction can be carried out using a fluorine-containing gas other than HF. The heavier Step III reaction products were separated from the CFC-217ba reaction product. The CFC-217ba reaction product included unreacted C3CI2F6. The mass balance results are shown below in Table 9. described above. These catalyst and reaction parameters are shown below in Table 11. As the results of Table 11 demonstrate various catalysts and reaction parameters prove useful. Particularly useful are iron, zinc and chromium chloride catalyst systems. The reaction products of the Step III reaction can be purified according to another process of the present invention. A process of the present invention is provided for separating C-3 chlorofluorinated compounds from a halogenation reaction product. The halogenation reaction products contemplated in this invention include the reaction products of Step III described above. This reaction product will include chlorofluorinated compotmds having at least three carbon atoms. According to one embodiment of the present invention, the halogenation reaction product includes CFC-217ba. Accordingly, a halogenation reaction product is provided which comprises C-3 chlorofluorinated compounds, HCl and HF. These types of halogenation reaction products will typically result from the halogen exchange of fluorine for chlorine on a chlorofluorocarbon. According to one embodiment of the present invention, the temperature of the halogenation reaction product is lowered sufficiently to separate the reaction products into at least three phases, including a upper gas phase containing HCl, a top liquid phase containing HF and a bottom liquid phase containing essentially acid free C-3 chlorofluorinated compounds. The temperature sufficient to separate the reaction product into at least three phases is from about 20°C to about 75°C. Preferably, the temperature is about 25°C. Like the separations previously described, the particular apparatus used for performing this separation is not critical. Examples of apparatus that would perform sufficiently include temperature regulated tanks and continuous phase separators. The process according to the present invention allows for the continuous ar.d/or batch separation of HF and HCl from C-3 chlorofluorinated compoimds. This is desirous in any industrial halogenation reaction scheme or small scale reaction scheme because it is often necessary to remove HCl and HF from the reaction product. Typically, this is a costly endeavor, requiring the separate stripping of the HCl and subsequent distillation of the HF. Example 16: Heterogeneous Phase Separation of C^CIF?: The fluorination reaction of HF and C3CI2F6 comprised a reaction product s"lieam containing approximately 40-45 weight % C3CIF7 and 50-55 wt % C3CI2F6 on an acid free basis. The reaction product was cooled and sent directly to a 3.9 liter liquid phase separation tank. The vapor pressure of the mixture in the phase separator was 6.5 Pa at 25°C. The reaction product separated into three phases. The top gaseous phase was primarily HCl gas. The bottom liquid organic phase was decanted off to be purified to produce essentially pure C3CIF7. The top liquid HF rich phase can be decanted off and pumped directly back as recycled HF, but for purposes of this example, it was discarded. The bottom phase contained mainly organics which measured 54 weight % CFC-216 and 42 weight % C3CIF7. The breakdown of the bottom phase composition is shown below in Table 12: products can be efficiently separated in a one-step process. This process is extremely useful because it negates the high costs associated with expensive multi-step distillation and separation techniques. Once separated according to this invention the reaction compounds can be used as final products or returned to a reaction scheme for further processing. According to the present invention the compounds thus separated have such high purity that they may proceed immediately to the next step without further purification. In accordance with still another process of the present invention, a halogenated organic compound is provided to be contacted with H2 and a catalyst to form a hydrodehalogenation reaction product. In a preferred embodiment the halogenated organic compounds are the Step HI reaction products which include CFC-217ba. Accordingly, the halogenated organic compounds are premixed with hydrogen and contacted with a metal containing catalyst at sufficient temperature to produce a hydrodehalogenation reaction product. In still another embodiment the hydrodehalogenation reaction products include HFC-227ea. A reaction of this embodiment is shown below: C5CIF7 + H2 -> HFC-227ea + HCl A slight molar excess of H; can be used if desirable but is not necessary. The f H::halogenated organic compound molar ratio is in the range of about 0.2:1 to about 10:1, optimally about 1.2:1. Refemng now to Fig. 6, the hydrodehalogenation is performed in fixed bed reactor 42 containing a suitable catalyst, such as palladium on a refractory oxide support, such as alumina or other suitable supports, in which case the reactor is operated at a temperature of about 30°C to about 275°C, and preferably at about 185°C. Alternatively, a feme chloride (FeCb) catalyst on a solid support, such as active carbon can be used in which case the reactor is operated at a temperature of about 200°C to about 600""C, and preferably at about 450°C to about 500=C. The pressure in reactor 42 should be in the range of about 1.2 Pa to about 15 Pa, and preferably about 7.9 Pa. The reaction is largely insensitive to pressure in the range of 0.9 - 7.9 Pa, however, reaction selectivity is slightly favored by lower pressures. Residence time in reactor 42 should be in the range of about 10 seconds to about 90 seconds, and preferably about 15 to about 60 seconds. While any hydrodehalogenation catalyst could be used, the most active catalysts, such as Pt and Pd, are good selections because, in addition to the desired products, they lead to the addition of hydrogen across any double bond present or to the substitution of hydrogen for chlorine. Catalysts which may be utilized include, as charged to the reactor, common hydrogenation catalysts such as Cu, Ni, Cr, Ru, Rh or combinations thereof It is not critical whether the catalysts are supported or not. However, supports which are unreactive to halocarbons, HF, and oxygen at hydrogenation temperatures up to lOO^C higher such as metal fluorides, carbon, and titanium, may be used. Referring now to Fig. 7, the high cost of noble metals led to concerns regarding catalyst lifetime. Initial testing demonstrated that the catalyst is somewhat fragile with activity dropping off within 5 days. Fortunately, it has been discovered that the addition of a small amount of water to the reaction stream extended catalyst lifetime. The addition of water allows the catalyst to perform in excess of 15 days. with no apparent loss of activity. The chemistry is not particularly sensitive to the amount of water present above a minimum of 0.8%. It has been determined that this process enhancement will test favorably with various catalysts. In one particular embodiniient, water was added to the H2 and halogenated organic compound and contacted with a catalyst. The additional water is from about 0.04 to about 12 percent by weight of the halogenated organic compound, and preferably, about 0.8 percent by weight of the halogenated organic compound. The previous description of the preferred embodiments will now be further demonstrated by way of non-limiting examples. Example 17: Step IV TC^CIF? -^ HFC-227ea: A 12.7 mm I.D. x 0.6 m long stainless steel pipe heated by an electric heater was used to combine materials as described Tables 14 and 15 and Fig. 7 below. The crude organic gas was then washed with water to remove acids and the gas was analyzed by gas chromatography. Table 14 demonstrates the results of this selective hydrodehalogenation with varying catalysts at varying temperatures. Table 15 demonstrates the extension of catalyst life according to the present invention. 17 above. It is clearly evident, particularly from Fig. 7, that the addition of water significantly increases catalyst life without affecting the conversion and selectivity. Like Steps 1, II and III control and reduction of the undesired isomer in Step IV can be achieved by selective reaction. Example 18 demonstrates this isomer control throughout the entire process when Steps I-IV are utilized in sequence. Of course the combination of the steps of the present invention include the following combinations: I, II and III (production of essentially isomerically pure CFC-217ba); and I, II and IV (production of essentially isomerically pure HFC-227ea); and I and 11 (production of essentially isomerically pure CFC-216aa). Data from a variety of sources has all shown that even at 90% conversion there is effective reduction of the isomer content. Example 18: Steps I-IV: Reactors of the type described in the previous example were placed in series and prepared as previously described. The specific reaction conditions are denoted in the Table 16 below. As Table 16 above demonstrates, the selectivity for a desired isomer at each step carries through when the steps are combined.. It is apparent that the four step process may likewise produce HFC-227ea via three steps by performing heretofore, Step IV following Step II. As shown above in Table 16 CFC-217ba is produced following Step II. According to another aspect of the present invention, a process is provided for the separation of a mixture of isomers of HFC-227ea and HFC-227ca. This mixture can come from different sources, however, it is contemplated the mixture will stem from a hydrodehalogenation reaction as described above. According to one embodiment of the present invention a mixture of these isomers is combined with a chlorofluorocarbon. Preferably, the chlorofluorocarbon is C3CIF7. This solution comprising the HFC-227 isomers and the chlorofluorocarbon are fed to a multiple stage distillation column operated under conditions such that HFC-227ea can be effectively distilled as a pure isomer. Distillation as it is known to those skilled in the art is a separation process in which a liquid is converted to a vapor and the vapor then condensed to a liquid. The latter is referred to as the distillate and the liquid material being vaporized is the charge or distillant. Distillation is thus a combination of the evaporation, or vaporization, and condensation. The usual purpose of distillation is purification or separation of the components of the mix. This is possible because the composition of a vapor is usually different from that of the liquid mix from which it is obtained. Alcohol has been so purified for generations to separate it from water, fuel oil, and aldehydes produced in the fermentation process. Gasoline, kerosene, fuel oil, and lubricating oil are produced from petroleum by distillation. It is the key operation in removing salt from sea water. Regrettably, isomeric mixtures cannot typically be separated by distillation. Embodiments of the present isomer separation process include the use of a ratio of chlorofluorocarbon to HFC-227ea from about 0.1 to about 10 and preferably about 1 to about 7. Upon distillation of this mixture essentially pure HFC-227ea is recovered as the distillate. The apparatus necessary to conduct this process will be apparent to those skilled in the art. Fractional distillation columns known in the industry will be readily useful to perform the process of the present invention. Example 19: Distillation Separation of HFC-227ea from HFC-227ca: To demonstrate the separation of HFC-227 isomers, a standard distillation apparatus was utilized and configured according to the parameters sho^v^l in Tables 17 and 18 below. As indicated, Table 17 demonstrates distillation with a chlorofluorocarbon and Table 18 demonstrates distillation without a chlorofluorocarbon. As shown in Tables 17 and 18, the addition of a chlorofluorocarbon significantly increases the ability, through distillation, to separate the isomers of HFC-227. The present invention also provides a process that selectively destroys undesired isomers, thereby increasing the overall isomeric purity in a mixture of isomers. According to one embodiment, this process includes providing a mixture of C-3 chlorofluorinated isomers. In another embodiment of the present invention, the C-3 chlorofluorinated isomers are CFC-216aa and CFC-216ba. In still another embodiment of the present invention, the C-3 chlorofluorinated compound isomers are CFC-217ba and CFC-2l7ca. Other isomer mixtures that can be purified according to the present invention will be apparent to those skilled in the art. In accordance with the present invention, chJorofluorinated isomers are heated in the presence of a catalyst to a sufficient temperature to reduce the amount of at least one of the chlorofluorinated isomers. The isomers are heated in the presence of a catalyst in like fashion to the reaction Steps I, II, and III described above. According to one embodiment the catalyst used is a chromium containing catalyst. A suitable temperature to increase isomeric purity has been foimd to be from about 250°C to about 350"^C. A more preferred temperature is about 280°C. By way of non-limiting example embodiments of this invention will now be demonstrated. Example 20: Selective destruction of CFC-216ba: In accordance with the present invention, a mixture of CFC-216aa and CFC-216ba was provided having a relative ratio of CFC-216aa to CFC-216ba of 96:U This mixture was heated in the presence of a pre fluorinated Chrom-gel® (provided by Englehard) catalyst at various temperatiu-es outlined below with the results shown in Table 19 below. Table 19. Selective Destruction of CFC-216ba Isomer As can easily be seen from Table 19 the process according to the present invention effectively doubled the ratio of preferred isomer, CFC-216aa, to the undesired isomer, CFC-216ba. The differences between the ratio determinations at 250° C are believed to be acceptable analytical error. To demonstrate still another embodiment of the present invention, non-limiting example 21 is provided. Example 21: Selective Destruction of CFC-217ca: In accordance with the present invention, a mixture of CFC-217ba and CFC-217ca was provided having a relative ratio of CFC-217ba to CFC-217ca of 81:1. This mixture was heated in the presence of apre-fluorinated Chrom-gel® catalyst at various temperatures outlined below with the results shown in Table 20 below. As can easily be seen from Table 20, the process according to the present invention effectively at least doubled the ratio of the preferred isomer, CFC-217ba, to the undesired isomer, CFC-217ca and in some instances more than quadrupled the ratio. Once purified in this fashion the resulting isomer is an excellent reactant for hydrodehalogenation according to Step IV of the present invention. In keeping with the selective destruction process previously described, a process for selectively halogenating specific isomers within an isomeric mixture is also provided. Isomer selective reactions play an important role when isomerically pure products are desired. According to one embodiment of the present invention a mixture of C-3 fluorinated isomers is provided and these isomers are contacted with CI2 in the presence of a catalyst at a sufficient temperature to halogenate at least one isomer. According to one embodiment of the present invention the mixture of C-3 fluorinated isomers contains HFC-227ea and HFC-227ca. It is contemplated that other hydrohalogenated compounds may be selectively halogenated according to this invention as well. Hydrohalogenated compounds suited for selective halogenation according to this invention will be obvious to those skilled in the art. According to still another embodiment of the present invention the catalyst is activated carbon. The specific type and preparation of the catalyst used to selectively halogenate are consistent with those catalysts described above in Steps I-IV. One aspect of the invention provides for the heating of the isomeric mixture to a sufficient temperature. According to one embodiment the temperature is from about 200°C to about 350°C. According to a more preferred embodiment, the temperature is about 300°C. According to still another embodiment of the present invention the molar ratio of C12 to the isomeric mixture is from about 0.16:1 to about 3:1 and preferably about 2.5. By way of non-limiting example 22, embodiments of the present invention will now be demonstrated. Example 22: Selective Halogenation of HFC-227ea: The specific quantities and types of reactants and the condition of the reactor utilized to demonstrate this invention are shown in Table 21 below. The reaction products were monitored for the isomers of CFC-217. As Table 21 demonstrates, the present invention can be used to even further reduce the content of the undesired isomer. It is contemplated that once reduced the more isomencally pure reaction product can be recycled or further refined. WE CLAIM; 1. A process for producing CF3CCI2CF3 comprising: contacting a saturated C-3 reactant comprising one or more of perhydrogenated or partially halogenated C-3 hydrocarbons with CI2 and HF in the presence of a first catalyst at a first temperature to form a C-3 product comprising a C-3 perhalogenated compound, wherein the first catalyst comprises chromium; and contacting the C-3 product with HF in the presence of a second catalyst at a second temperature different from the first temperature to form CF3CCI2CF3 wherein the second temperature is greater than 300°C. 2. The process as claimed in claim 1 comprising contacting the CF3CCI2CF3 with HF in the presence of a third catalyst at a third temperature to form CF3CCIFCF3. 3. The process as claimed in claim 2 comprising contacting the CF3CCIFCF3 with H2 in the presence of a fourth catalyst at a fourth temperature to produce CF3CFHCF3. 4. The process as claimed in claim 3 comprising, during the contacting of the CF3CCIFCF3 with H2 contacting the fourth catalyst with water. 5. The process as claimed in claims 1, 2, 3, or 4 wherein the first temperature is from 150°C to less than 450°C and the second temperature is less than 550°C. 6. The process as claimed in claims 1, 2, 3, or 4 wherein the first temperature is at least 220°C and the second temperature is at least 470°C. 7. The process as claimed in claims 1, 2, 3, or 4 wherein, during the contacting of the C-3 reactant with the HF and the CI2, a molar ratio of the HF to the CI2 is from 0.75:1 to 8:1. 8. The process as claimed in claims 1, 2, 3, or 4 wherein, during the contacting of the C-3 reactant with the HF and the CI2 a molar ratio of the HF to the CI2 is at least 4:1. 9. The process as claimed in claims 1, 2, 3, or 4 wherein, during the contacting of the C-3 reactant with the HF and the CI2 a molar ratio of the CI2 to the C-3 reactant is from 8:1 to 10:1. 10. The process as claimed in claims 1, 2, 3, or 4 wherein the second catalyst comprises chromium. 11. The process as claimed in claim 2, 3, or 4 wherein the third temperature is at least 200°C. 12. The process as claimed in claims 2, 3 or 4 wherein, during the contacting of the C-3 product with the HF, a molar ratio of the HF to the C-3 product is at least 30:1. 13. The Process as claimed in claims 2, 3, or 4 where during the contacting of the CF3CCI2FCF3 with the HF, a molar ratio of the HF to the CF3CCI2FCF3 is at least 10:1. 14. The process of claims 2, 3, or 4 wherein the third catalyst comprises chromium. 15. The process as claimed in claim 3 or 4 wherein the fourth temperature is at least 30°C. 16. The process as claimed in claims 3 or 4 wherein, during the contacting of the CF3CCIFCF3 with the H2 a molar ratio of the H2 to the CF3CCIFCF3 is at least 1.2:1. 17. The process as claimed in claim 3 or 4 wherein the fourth catalyst comprises palladium. 18. The process as claimed in claim 4 wherein the water is present in an amount from 0.04 to 12 percent by weight of the CF3CCIFCF3. 19. The process as claimed in claim 20 wherein the amount is 0.8 percent by weight of the CF3CCIFCF3.

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0620-chenp-2004 form-6.pdf

0620-chenp-2004 others document.pdf

0620-chenp-2004 others.pdf

0620-chenp-2004 pct search report.pdf

0620-chenp-2004 pct.pdf

0620-chenp-2004 petition.pdf

620-CHENP-2004 DESCRIPTION (COMPLETE) GRANTED.pdf