CA2614530A1 - Materials and methods for the production and purification of chlorofluorocarbons and hydrofluorocarbons - Google Patents

Abstract

There is provided a hydrogenation process comprising contacting a compound with a catalyst in the presence of water to form a hydrogenated compound preferably the contacting further compounds contacting the compound with H2. There is also provided a process for purifying CF3CFHCF3 comprising distilling a mixture comprising CF3CFHCF3, CF3CF2CF2H, and at least one chlorofluorocarbon to form a solution comprising CF3CFHCF3. There is also provided a process for purifying chlorofluorinated compounds comprising: providing a reaction product comprising HCl and/or HF, and a at least C-3 chlorofluorinated compound; phase separating the reaction product into a gas phase comprising the HCl, a top liquid phase comprising the HF, and a bottom liquid phase comprising the C-3 chlorofluorinated compound; and removing the bottom liquid phase to form a solution comprising the C-3 chlorofluorinated compound. There are also provided other related processes for separating, purifying and/or halogenating compounds such as chloro or hydro fluorinated compounds.

Description

MATERIALS AND METHODS FOR THE PRODUCTION AND PURIFICATION
OF
CHLOROFLUOROCARBONS AND HYDROFLUOROCARBONS
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 halo~enated hydrocarbons.
BACKGROUND OF THE INVENTION
Since the beginninc, of global warminp 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 floodina acyent, extin~uishant, propellant and refri-erant production industry a dvnamic and ever-chan~ing marketplace where processes for the production of chiorofluorocarbons and fluorocarbons are advancing, quickly to accommodate both environmental as well as econornical requirements.
Some useful compounds in this area include both saturated and unsaturated fluorocarbons, such as I,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=CF,. FC-1216). One well known method of svnthesizing these compounds begins with the chlorofluori nation of propane, propylene or partially halogenated C-3 hydrocarbons with hydrooen fluoride (HF) and chlorine (Cl,) in the presence of a metal-containin- solid catalyst. Examples of this chlorofluorination step can f.ie found in U.S. Patents 5,057,634 and5,043.491 to Webster. As tauaht by Webster, the chlorofluorination step produces a number of saturated perhalocrenated chloi-ofluoT-ocarbons, includin2: (A) C_Ci;F;: (B) C;Cl4F4; (C) C;CI;F;; (D) 1,2-dichlorohexafluoropropane (CF3-CCIF-CC1F2. CFC-216ba); (E) 2,2-dichlorohexafluoropropane (CF;-CCI2-CF;. CFC-? 16aa); (F) 1-Replacement sheet 1, Under Article 34 WO 03/029173 PCT/I;S02/30729 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 Cl2 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 C3C12F6 (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.

~'ILE
D
~
~ f~~C 0 6 2007 SUMivtARY OF Iiv-VENTION

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-216aa intermediate by chlorofluorinating C-3 reactants with HF
and CIz without the formation of substantial or even detectable amounts of FC-218 or undesired isomers.
In one embodiment the present invention provides a process for producing CF3CC12CF3 comprising: contacting a 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 the first temperature is less than 450 C; 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 CF3CC12CF3 wherein the second temperature is greater than 300 C, the CF3CC12CF3 product comprising a mole ratio of CF3CC12CF3 to CF3CFC1CC1F2 greater than 2:1; contacting the CF3CC12CF3 product with HF in the presence of a third catalyst at a third temperature to form CF3CCIFCF3;
and contacting the CF3CCIFCF3 with H.) in the presence of a fourth catalyst at a fourth temperature to produce CF3CFHCF3].
In accordance v,-it.h 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 unexpectedlv high yield of CFC-216aa without the fot-mation of FC-2I 8.
One aspect of the present invention is to provide a method of manufacturinc, a CFC-216aa intermediate by ehlorofluorination of C-3 reactants such as aliphatic, olefinic or partially halogenated hydrocarbons having at least three carbon atoms, wherein the process provides ne~i and unexpected selectivity for the CFC-216aa reaction product.

rlnother aspect of the present invention provides a method of manufacturing a CFC-216aa intermediate for prepanng 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-2 17ba to produce HFC-227ea by contactin; CFC-217ba with HZ 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 subsequentlv separatina, the mixture by distillation. In one embodiment the chlorofluorocarbon is CFC-2 I 7ba.
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 halooenation reaction product includes CFC-216aa.

FILE-U
DEC 'j 6 2007 ~ -~
4a Still another process for separating halogenation reaction products is provided herein the reaction products are combined with water and cooled to a sufficient temperature to form a Qas phase and top and bottom liquid phases. Accordino to one embodiment, the cyas phase contains pnmarilv C-3 chlorofluorinated compounds havina at least six fluonne atoms, the top liquid phase is primaril%- an aqueous liquid phase and the bottom liquid phase contains C-3 chlorofluonnated compounds having less than six fluorine atoms.

An additional process according to this invention provides for separating C-3 chlorofluonnated 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 aas phase and top and bottom liquid phases, wherein the upper oas phase contains pnmarily HCI, the top liquid phase contains HF and the bottom liquid phase contains essentiallv acid-free C-3 chlorot7uonnated compounds.

In still another process of the present invention methods are provided for svnthetically increasin2 the isomeric puntv of a mixture. According to one embodiment, an isomeric mixture of C-3 chiorofluonnated compound isomers is heated in the presence of a catalyst to a sufficient temperature to increase the isomeric puritv. In a more specific embodiment, the C-3 chlorofluorinated compound isomers are CFC-217ba and CFC-217ca.

In still another embodiment of the present invention a process is pro,,ided for selectively halogenatina isomers Nvithin an isomeric mixture. In a particular embodiment, the isomeric mixture is exposed to Ck in the presence of a catal~st at a sufficient temperature to halocrenate at least one isomer. Preferablv the isomeric mixture includes the isomers HFC-227ea and HFC-227ca.

The abo%e and other embodiments. aspects, alternatives and advantages of the present invention will become more apparent frorn the following detailed description of the present invention taken in conjunction with the dra\~ings.

Replacement sheet 5. Under Article 34 DESCRIPTION OF THE FIGURES
Figure I 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.
Fiaure 3 is a block diagram of an embodiment of the present invention.
Fiaure 4 is a block diagram of an embodiment of the present invention.
Figure 5 is a block diagram of an embodiment of the present inventi.on.
Fiszure 6 is a block diagram of an embodiment of the present invention.
FiQure 7 is a graphical representation of catalyst life observed accordina to an embodiment of the present invention.

Replacement sheet 6, Under Article 34 = WO 03/029173 PCT/US02/30729 DESCRIPTION OF THE PREFERRED EMBODINIENTS

Referring now to Fig. 1, in one embodiment this invention provides processes for the production of chlorofluoropropanes and fluoropropanes from aliphatic, olefinic, or partially halocenated hydrocarbons havina at least three carbon atoms. Other embodiments of this invention provide specific processes for hydrodehaloaenation, as u-ell as, isomer and reaction product purification. Selected embodiments of this invention will be descnbed in turn be-inning with the broad chemical process steps used to produce selected chlorofluorocarbons and fluorocarbons.
In part, this invention stems from the discovery that the maionty 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 dov, nstream counterparts are passed to subsequent reactions underLyoinc, the same chemical transformation as the desired isomeric material. Fortunately, CFC-216ba and its down-stream counterparts, have different reaction profiles allowing for their reduction %wh each s'-,bsequent step. Unlike CFC-217ca and HFC-227ca, CFC-216ba is not a "dead end" isor-~:.-r. A majonty of this material is directly converted to the desired isomer CFC-? 17ba in subsequent steps performed in accordance with the present invention.
Without bein'a confined to any theory, the formation of the undesired isomer takes place in these early reactions by the premature fluonnation of the Qeminal C-2 carbon of aliphatic, olefinic, or partially halogenated hydrocarbons having at least three carbon atoms. The production of CFC-216ba is but just one example of this type of chemistry.
Referrin2 now to Fi2. 2, formation of excess amounts of CFC-? 16ba durina halo2enation has been observed when the reaction is allowed to e\otherm excessively.
The larze amounts of energy released dunng this exotherm are probably the ultimate reason for Replacement sheet 7, Under Article 34 = WO 03/029173 PCT/US02/30729 excess CFC-216ba 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 halo~enations 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 enaineerinQ controls to insure suppression of exotherms. In another aspect of the present invention. HF can be replaced as the main diluent for the reaction. Figs. 3-=1 show a schematic flow diasiram for a process accordina 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 chiorine in the presence of a chlorofluorination catalyst. The process is highly selective in the production of CFC-216aa, without the formation of any siQnificant amount of FC-218 (0 to less than 0.5 percent by w=eiaht). The high yield and selectivity of the process of the present invention in the synthesis of CFC-216aa is very advantaoeous for the subsequent production of HFC-227ea as discussed below.

The present invention provides, in one aspect_ t%~ o step processes for efficiently producinc, CFC-216aa. The chemical steps can include the sequential replacement of hydrogen with chlorine and the subsequent partial replacement of chlonne with fluorine atoms. Multiple products may be formed with intermediate fluorinated materials bein-, 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 beinc, chlorine. The cracking of the C-3 backbone to form C-I and C-2 matenals as undesired impurities has also been observed. According to one embodiment, the output of this reactor can be fed directlv into a subsequent reactor as shown in Fi2. 4, which is run at a higher temperature. Individual reactants may be fed under flow control to vaporizer(s) 14, as shown in Fi'. 3. Thc vaporized chlorine and HF are niixed and fed into a superheater. It has been determined 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.
Replacement sheet S, Under Article 34 The predominant reaction occurring in exemplary chlorofluorination Steps I and II
may be summanzed, as follows, with high selectivity in the production of CFC-216aa:
CH3CH,CH3, CH3CH=CH, and/or C3H,XZ+HF+CI2-CFC-216aa+HCl (X=haloQen; y=0-8, z=8-y; or y=0-6, z=6-y) Accordins! to one aspect, the process includes a first step, wherein C-3 reactants selected from the Qroup consisting of aliphatic. olefinic or partially halo-qenated hydrocarbons havinlc, at least three carbon atoms are contacted with Cl, and HF in the presence of a metal containin- catalyst_ As illustrated in Fig. 3, this reaction is preferably performed in the gas phase by the careful mixinR of C-3 reactants with a mixture of hydro-en fluoride (HF) and chlorine (Cl,) 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 ,cYroup consisting of aliphatic, olefinic and/or partially halocenated hydrocarbons. The C-3 reactant mav be premixed with hydrogen fluoride, and then mixed with chlorine before enterina chlorot~uori nation reactor 16 containing a fixed bed of metal containina 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 havinl-at least three carbon atoms are known to those havin-a ordinary skill in the art to be unsaturated aliphatic hydrocarbons havina at least one double bond. These types of compounds include propene. Partially haloQenated hydrocarbons having at least three carbon atoms are known to those havin'- ordinary sk.ill in the art as aliphatic or olefinic hydrocarbons wherein one or more hydrogens have been replaced by haloaens.

Accordinlg to one embodiment of the present invention, the HF and C-3 reactants are premixed before being combined with the chlorine gas and conveyed into a chlorotluorination reactor. It is preferred to preniix (dilute) the C-3 reactant with the hydrogen fluoride reactant prior to combinin'- the HF/C-3 Qas reactants %k ith the chlorine 2as reactant in ordei- to mininiize the potential reaction of the C-3 reactant, e.g., propane and/or propylene with concentrated chlorine sias. 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 ',-ith the chlorine gas.
Replacement sheet 9, Under Article 34 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 recoQnized bv those skilled in the art. The Cl, likewise is a matter of choice to those having skill in the art. In one embodiment, technical or pure-grade anhydrous Cl, is utilized.

The halogenation of aliphatic, olefinic, or partially haloaenated h%drocarbons havinc, at least three carbon atoms is a highly exothermic reaction which ma~
be controlled throuah the use of excess quantities of hvdroaen fluoride, a diluent, or an eYternal 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 erotherms, preferably, a stoichiometric excess of hydrogen fluoride mav 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 chlorine aas as well, preferably about 8 to about 10 moles of Cl, per mole of C-3 reactant. Ho~~ever, an excess of Cl, is not required. In a preferred embodiment. the ratio of Cl, to C-3 reactants can be about 8.2:1. The molar ratio of HF to C1, may be from about 0.75:1 to about S:1. Preferably, the molar ratio of HF
to Cl-, may be about 4:1. Moreover, in another embodiment, a diluent may be added to the reaction to decrease undesired isomer and formation of crackin!z materials.

Preferably, the chlorofluonnation reactor 16 used to perform this in~ention may be maintained at a reaction pressure of about 0 psig to about 750 psiQ, preferably about 0 psig to about 750 psig and at a temperature in the ranae of about 150 C to about 450 C, and preferably about 220'C. Residence time in chlorofluorination reactor 16 may be in the rans!e of about 0.5 seconds to about 30 seconds and preferably about 5 to about 10 seconds.
An exemplary reaction miXture exiting Step I sho~~n in Fio. 3 is nch in C:CI_F, and C;C1;F;, but may also contain CFC-2 16aa and many other under fluonnated compounds.
In an exeniplary aspect, reaction products of this first step are conveyed directly to Step II, as shown in Fig. 4. However, it is recognized that the reaction products of Step I. as shown in Fi2. i, may be further purified or supplemented prior to continuinQ
on to Step II.
A main Qoal in Step II can be the selecti%e fluorination of under-fluorinated compounds to the desired isome-- CFC-2 l6aa.

Replacement sheet 10, Under Article 34 - ,....
= WO 03/029173 PCT/US02/30729 In the illustrated embodiment, the second step in this process may replace all of the terminal chlorine substituents with fluotine to produce CFC-216aa. Accordinc., to one aspect of the present invention, this is accomplished throuqh the use of one or more of hiah temperature reaction conditions, excess HF. and a metal containing catalyst.
As shown in Fia. -l, the Step I reaction stream is directly fed into a superheater 24.
Optimally, this stream is then fed to Step II reactor 26. AQain. 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.
According 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%ina a metal containinq 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 530 C, and preferably at about =170-C. It is preferred that the molar ratio of reactants in Step II, should be maintained at about 6 to about 64 moles of hy-drogen fluoride per mole of perhalogenated compounds. As in Step I, the source and quality of anhydrous HF
used in Step II is not cntical. It is to be understood by those skilled in the art that anhydrous, recycled, and/or differing arades of HF can be used in Step Il. As in Step 1, a diluent may be added to control exotherms and increase isomeric yield.
The metal containinQ catalyst used in Step I or Step II can be any known catalyst useful for reactin- C-3 reactants or perhalogenated compounds with HF and/or Ck, including those described in U.S. Patent Nos. 5,177,273 and 5,057,634 to Webster These catalysts include catalysts consisting essentially of chromium: catalysts consisting essentiallv of chromium oxide in combination with a support (e_o, refractor%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 froni the Qroup consisting of manqanese, iron, cobalt, nickel, copper, zinc, other metals and mixtures thereof; and catalysts consisting essentially of chromium oxide in combination %t ith the refractory oxide and modified with up to about 10 percent by weight based tupon the r .
WO 03/029173 PCT/1; S02/30729 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, CC13F, CC1-2F2, CHF3, or CC1,F-CC1F2) at elevated temperatures. Pretreatment of catalysts containing refractory oxides such as alumina are considered particularly 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 oxvchlorofluoride 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 the scope of this invention.
In this and the other reaction sequences, reaction with HF ir:ludes either high temperature vapor phase reaction or lower temperature reaction in T:-.z presence of a liquid phase catalyst such as SbCI;/I-IF or SbF5: the vapor phase process is preferred.
Two metal containinc, catalysts that have been found to be r~rticularlv useful for the chlorofluorination reactions include:
(1) FeC13 on a support, particularly active carbon, that is dr.~d and then tluorinated, e.o., with HF, preferably an HF/i\1, mixture, with or %ti ithout O-', at :::bout ?00 C to about 270 C and then treated with HF, with or k%ithout O, or CI, activatio;;. within the ranae of about 270 C to about 320 C. It is preferred that the percent by we"ht of FeCl;
in the metal containinga catalyst be in the range of about 29c to about W"c b,, weight on a catalyst support, which is preferably activated carbon, preferably at about 5_c to about 10% by weight FeCl3. It is useful to fluorinate the metal containinc, cataM: for a peried of at least about 2 hours, preferably about 2 to about 16 hours. more preferabi,: about 8 hours, qradually increasin-, the temperature kk-ithin the rage of from about 2O0 C to at least the chlorofluorination reaction temperature, e.g.. up to about 320 C; a,-d (2) CrC13, particularly chromium chloride hexahydrate (CrCI_ = 6H,0) on a support, particularly active carbon, that is dried and then fluorinated. e.g., with hydro-en fluonde gas (HF), in the same manner as fluorination of the FeCI; catalyst %vith or without 02 or Cl? activation.
Non-limitin(z examples 1, 2 and 3 :~ demonstrate the prepara_:,-_)n of catalysts suited for the present invention and non-limitinsi example 4 demonstrates ~he activation of catalyst suited for this invention.

Generally, all fluorination catalyst can be prepared by mix:7.g appropnate amounts of the selected metal salt and support (if necessary) in DI Water. T:~is mixture may be allowed to stand for appT-oximately 0.5 hour and the e,~cess water be filtered off by vacuum filtration. The resultinL, solid mav then be dried overnicl:: in a oravit% oven at 1 13 C and then char2ed to the reaction tubes where it can be furt~.:r dned at 1~0 C with a inert aas pur2e and then activated with HF before the reaction feec:S are started_ Replacement sheet 13, Under Article 3-4 Example 1: FeCII/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: CrCI;/Activated 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: NiC12/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 Catalyst Activation Methods:
The chlorofluorination catalyst was activated using a chlorofluorination reactor with HF. The foilowing description gives the detailed procedures for three methods of chlorofluorination catalyst activation.

(a) The FeC13/carbon catalyst of Example I was added to both Step I and Step II
reactors and the catalyst in each reactor was dried with N, 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 11 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 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/N12. The metal containing catalyst was further activated with 2% by weight 02 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 02.

WO 03/029173 PCT!US02/30729 (c) The same procedure was performed for the catalyst activation as described above in method (b) except using 2% by weiQht C12 instead of 2% by weight OZ.

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 chlorofluorination, according to the present invention.

Example 5: Chlorofluori nation of C-3 Reactants:
Step I was conducted according to the parameters indicated in Table I 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 1, Step II was performed with a fixed-bed reactor containing a metal containing catalyst. The specific types of catalvst are described in Table I
below.
The hydrogen fluoride used in Step I and Step II was anhydrous liquid HF that was vaporized to provide anhydrous HF eas. The results of the present example are shown below in Table 1.

. .~;

N
U
c:.
U
~
= U
U oo c~ ~a ~ o N c~ oo r~i U
N
.r O
E
~ '- p ~ oo G1 M
C/) U
c -Ci.
.:) R v o 0 0 cn U oc 00 U U
r Q~
m v~ U N

2 O E ~t o0 U
=3 0 C C
cn ~ G
O O o C ~ p cJ V O O O
C/]
rO ~
U
pV o o 'v ca c~ E~: N -E:;

~
3 c~ v, ~n o N N
LG.r, o~c G~
C ~ M ~
~!1 M b ~1. u o o cn ~
a~
-ts v =v Z;
f'1 ; Q i'1 ; Q N > 0 ~
y =~ ~4 ...~ _ ~y t0 u U p U U ~ U U ct7 Uc: ~UUUZU C

As demonstrated in Table I above, iron and chromium chloride catalysts are particularly well suited for use as metal containinV catalysts according to the present invention. In particular, when utilizinLy the iron catalyst no detectable levels of the undesired CFC-216ba isomer were found.

Non-limiting 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:C12:C-3 reactant, 6:9:1. Residence time in the Step I reactor was about 10 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-2I6aa, hydrogen fluoride and hydrogen chloride gas, and were conveyed into a central portion of a strip column for HCI removal.

The chlorofluorination 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.

~= _, .

Table 2. Mass Balance of Reactants and Products of the Present Invention Total Feed Materials C3Hs 3.1 kg Cl') 46 kg HF 8.7 kg Total Products Collected HCI 41 kg C3CIZF6 11 kg Underfluorinated compounds 3.4 k~
Recovery -95%
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 Varving Starting Materials and Reagent Proportions:
Tandem InconeV 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 Clz 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 HCI, C12 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 C3C1ZF6 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 (C3H8, 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 effdt"ts of additions of a diluent are shown below in WO 03/029173 PC'i'/US02/30729 Table 4. The exotherms observed during run conditions dictated in Table 4 are demonstrated in Figure 2.

-- ~1 .
WO 03/0_9173 u Q 'Q Trl \=~ v N '. M V V
M
hh " N ~ - o vJ I ~o~ u C

I U
~
-= 3 u ~+ c v U .o c' o!J c- OC o _N cc~ x E1 J I v v E
.~ o ce U U ..:~
~ N N"" L:. M N y ~' S) co v ~ C h N ,T . C N I~ y vCi ~ ~n = P. N .-~ C~ N v U N N VN N

y N ~
dj y aC~ r3 C y 00 r-~ N r. N N~ ~ _ = M _ E c3 ~CV M 0 U M M

T =
O y ~
C r- N C ~ \O Q, ;
~ _ =~
LL " ~
E .T. ~oo~ y 3 ci N c c w : >
~++ vf ~'~J ~O OC 00 00 ~ M
U
v Cs v N
{r C'~~ =U

~' ~~ o a o a y E
o U
~" C N
c:
v v cs U >
N N 0 C.v N N N N -0 ~
?~ r.=~ =V
cr C
n C
CZ
= G n 0 U a O
K U
U

N
U
F U
~~ R o0 ~'f N O= ~
h N ~l (~ 00 r'1 V m >

~ z N o u' c Q x U
1 U o v - y z Q 2 o ~ E~-~ 0 =O

(Sa p0 v;vN; ~
C'+
2 u~ M ri ri ri ri ~ ~ t/]
r>
C7 a [
o - o 0 o U
W U Q Q ? o 0 0 o t.~.. CJ

i>
o- .,~ ~ ~ o o n o ~ a~
S o 0 0 _ o o ~ ~ N
O
z Oa _ .
~ ~ a Q c~ , _U -_C
'-b O
v v ~ LJ U n oo _ .. ~ P .. c';S
~ O~ Q Q '~ r Q ~ n G. CJ
Z z X p'o O Oen C ~, n O~ = Q N o 3 cti q ~u:~ .~J C
I U Z~ ~ N I~ _ VJ

~ a VF-~ oc~ o ~~ oN o OC E
U U

L7 ~T
Q o po p o o U _U
'~- rv N rõ o o ry o >
~' O cp u a m c7 o~~ oLL.c tt N
c'JNUC'+ NV ~ c C~ U
z O b0 h Q .[
~
~C -cd ' 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/C3H8 mixture and C12 in another mixer before the Step I
reactor; and (2) first mixing the HF with ClZ using a static mixer, and then adding the HF/C12 mixture to C3Hg in another mixer before the Step I reactor. The reaction parameters and results of this example are listed in Table 5 below.

N r, .
UV\ oo~ ac*
=.' c~ o c c ,-.
~ No 'n U cs c, V:
~
c u 'i, C
>
" V-, V, 00 ,: o M o"
y C~ ~ l- ci oo c~
~ ~r M ~Y M M
Qr ~-.

UNt- aN a, _ ~ o oa o0 U
Q co 3 U E o oo ~D vi ~r G:r M C'~1 M M

~.
~ x~~ J O M
V, - M C CJ~ ~D
~+ ~t O f V C~1 C M M tr1 M

Cy L
~ .7 rti N
v ~./
00 00 Oo 00 00 U
.=, -.o c c Ln V"~ ~ ~
~.. o 0. v U i N N~ N N
~ ~ C C
*o 00 00 00 . ~ ._ -- !'.' " . = , WO 03/029173 PCT/US02; 30729 As Table 5 demonstrates, the combination of reactants plays no role in the overall selectivity of C3C12F6. 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 HF 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 temperature 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 chiorofluorination reaction products) is removed to obtain essentially or?anic 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 distiliabon processes and the production of HF/chlorofluorocarbon azeotropes are discussed in U.S. 6,211,135 to iviiller, 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 chiorofluorination reaction product including HF, Cl2 and CFC-216aa was purified according to the present invention. The reaction feed stream included 0.04 k!z/s C12 , 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 HCI 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.

:.-.~ .

Table 6. Chlorofluorination Orsanic Phase Removed from HF AccordinQ to a Process of the Present Invention Area % CI2 Area % HF Area fc HCI Area c Oraanic Separated 1.21 0.3872 0.6097 97.79 Orsanic Phase Table 7. Halogenated Organics Separated from HF According to the Present Invention Halogenated Oraanics Percentaae of Total Organics CC13F-CCIF3 not detected Liahts 0.05 C3CI-'F6 64.59 C3C13F5 11.83 C3C4F4 5.75 Heavies 3.65 As this example demonstrates the organic phase, once separated accordincr to an embodiment of the present invention, is essentially acid-free. This allows for the immediate isolation of specific chlorofluorination reaction products without the need for costly and inefficient distillation. Moreover, Table 7 demonstrates that other halogenated oroanics can be separated from HF, according to the present invention. These chlorofluori nation reaction products can be isolated accordina to another process of the present invention as herein described next_ Another process accordin- to the present in~ention is the separation of the C-chlorofluorinated compounds havina, at least six fluorine 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 comprisinIg C-3 chlorofluorinated c:ompounds havinq at least six fluorine atoms and C-3 chlorofluorinated compounds havinc, less than six tluorine atoms is provided. This solution is derived from a reaction product or a refined reaction product of a chlorofluonnation reaction or the phase separation or distillation product after a chlorofluorinated reactiorl. In one embodiment of the present invention the C-3 chlorofluonnated compounds having at least six fluorine atoms comprises CFC ? 16aa. However. this invention is not limited to the source of this mixture.

Replacement sheet 26, Under Article 34 WO 03/029173 PCTiUS02/30729 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 chiorofluorinated 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 leavinb behind or allowing for the removal of the top aqueous phase. Upon removal, these phases can be further processed or retained as end products. According to one embodiment of the present invention, the ~ WO 03/029173 PCT/US02/30729 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 C3Cl-)F6 from various production runs of Steps I and II
contained C3Cl2F6 and numerous other unidentified underfluorinated compounds, and possible small amounts of H,O, HF, Cl-), and HCI.
Approximately 73 kQ of crude C3Cl2F6 were fed from a heated cylinder to a 57 liter Halar~ lined scrubber tank. The scrubber tank contained a level -auae and an external heat tracinc, with a skin temperature thermocouple. The feed line into the tank was throuah 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 Qaseous 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 Sas was open to a molecular sieve dryer bed v"hich fed into a chilled collection eylinder on a scale. Upon completion of the scrubbinc, of the C;C]-,F6, the underfluorinated oroanics collected from the bottom phase was approximately 9.1 ka of material. The primary components of this oraanic liquid were C3C14F4. and C3C13F5 and C3C1,Fb.
Table 8. Results of Separation of Underfluotinated Separation .accordinQ to the Present Invention Separated Phase Constitutents Vapor Essentially pure C;CI,Fb Bottom -69c C3C1,F6 and -94% underfluorinated compounds As table 8 demonstrates, underfluorinated compounds can be efficiently separated from C;C1,F6 according to the present invention.
As shown in Fi2. 5, the present invention provides a thit-d reaction step (Step III) for the selective fluorination of C;CI~F6 to CFC-217ba. The predominant reaction occurring in this step is as follows:C3Cl,F6 + HF - CF3-CFCI-CF3 + HCI
Preferably, Step III proceeds in the gas phase %vith excess anhydrous HF over a metal containin2 catalyst. Accordincy to one enibodiment of the present invention.
Replacement sheet ?S, Under Article 34 ~

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 wil! 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-216aa 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 hvdrogen fluoride.
Preferred catalysts for the synthesis of CFC-2I 7ba are supported metal containing catalysts. Metals such as iron, zinc, chromium and mixtures thereof are particularly useful as catalysts for the conversion of C3C12F6 to CFC-217ba.
Acceptable results can be obtained w-ith 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 02 or C12 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 catalvst is dried with N2, fluorinated with HF/N2 at 250 C for 9 hours.
The catalyst is th& further activated with HF/Nz 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 02 along with HF/N2 for 12 hours, then another 2 hours without 02.

(c) The same procedure for the catalyst activation as described above in method (b) is used except using 2 ro by weight C12 ir.stead of 02.
Non-limiting examples I 1 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.
ExamDle 11: FeCI:/Activated Carbon Catalvst:
Iron (III) chloride hexahvdrate (3.78) moles was dissolved in deionized water (1000 cc). The solution was mixed into and absorbed by 1000 erams of active carbon pellets and air-dried overnight.

Example 12: CrCI3/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 ovemight.

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 FeCl3/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;N, 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.
(b) The same procedure discussed above in method (a) was performed for metal containino catalyst drying with N, and fluorination with HF/N2. The metal containing catalyst was further activated with 2% by weight 0, 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 IVvithout 02.

~ ~~

. . - - .~

(c) The same procedure was performed for the catalyst activation as described above in method (b) except using 2% by weight ClZ instead of 2% by weight 0,.
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 (C3C1,F~ -+ CFC-217ba): -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 HCI, 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 C3C12F6.
The mass balance results are shown below in Table 9.

~1 /~
= ' WO 031029173 PCT/US02/30729 Table 9. Mass Balance Results Total Feed Materials: C3CI2F6 (99.7%) = 9.4 kQ
G
HF = 0.9 kg Total Products Collected: HCI = 1.2 kg HF = 0.13 kg C3CIF7 = 4.1 kg C3C1ZF6= 3.3 kg Recovery 84.8%
As is demonstrated above in Table 9, approximately 85% of the reactants are recovered as products that can either be further refined, recycled or purified.

Non-limiting example 15 demonstrates the impact of the catalyst selection on the process of the present invention.
Example 15: Comparison of Catalvst The Step III reaction was performed as described in Example 14 above with the exception that the catalyst parameters noted in Table 10 below were utilized.
Over a 12-hour period, multiple reaction product samples were taken. The average C3CIF7 selectivity is shovm in Table 10 below.
Table 10. Averaee C3CIF1 Selectivity % (12 hours averaqe) Chromium Oxide Chromium Chloride Activated by Activated by Activated by Activated by Activated by L method (a) method (b) method (c) method (b) method (c) 82.74 82.29 84.10 76.19 81.40 As seen from these results, the Step III process according to the present invention selectively fluorinates the desired C3CI2F6 resulting in increased production using catalysts of varying chemistry and activation.
To fur,her demonstrate the flexibility of fluorination according to the present invention, numerous catalysts were employed. These catalysts were prepared following the same general preparation methods detailed in examples 1 throuah WO 03/029173 r,/~ PCT/US02/30729 s described above. These catalyst and reaction parameters are shown below in Table 11.

.. ~ ~ .
W O ,~3/029173 PCT/i,,'S0:/30729 a m O v~Oi O a O ~~O a O T n vOi vmi '"~ s P~ N
f1 LL O N-= N õmõ P N e+i O r~i :2 O~ v v~ N %O n ~ f't v1 U
A
L
~ n N O O N Q ~ r m' 7 R N ~ C1 N~ N N Q Q' U l- en Q, x N O m~~ O 1+ ~ N N t'1 0 Z C
ry U
b T -+ N IY 10 10 i O O~D V1 O N ~'d Q O~ N~D v1 N -+ N f+1 N ~n N ~O N P r1 m N N V ~"~ N h N ~ O~ N V O~ X n P1 n O~ N a0 O
r vi OC rV m e~1 I~ N:.'s O 0 ~O N n m O. V~ ~G ~ v1 fV ~f Q
U F R r n V' F F F P1 ~ P r ~/1 ~O ~/1 ? N ~O - ~O
U

zC - ao v, m a N o m'n n.-, n-v, n v v n --~o o P n ~ u O m 70 ~O v-~ m ~~O V r~ m 7.n ~D oD ~O N v~ N N vi m ~~L
~ 'Q7 () -~O O C C O O O C O O~G C O C O~ ~"~ ~-+ O C C
y ~ U
~ o b ~' v n N ty1 N rn N F ~O O+ N O o0 m vi N v~ .~r O m e~ t'~G'1 N r N O N~ N~p m "O O O vi O O m m O~ ~-. O _ O f~l 00 M~~= O~~O O~ O R 0~ vi ei 0% T 00 vf f~ Vi N N
~j M v~ v~ r~O P1 P tV P1 v+ n n r ~
E U
Y
y~ N
V, v~O n N~n ~O P Ol F N O O C~ 'O e N ? r Ol 10 14 ON O
O~- N O n O OlO N n O v rl r O c'O ~'1 N
O O O O O C O O O O O - O O O O O O o O O O O N O
U
m O - O O ? O~ o N ~O n 0 f~1 r O 10 n n ~ N o m O o o rf O o O 7~n O O -Ly, C e+1 O C C C O C O O %0 O O C O O O C O O 0 ~ O Q
o N %O v'f R O -~ ri '0 ? '0 -'= O ~O m %O o0 O -+ m N F m O ~O Q O ~f ~O o0 N v O~ 7 2 ~ j o= G o 0 0 0 0 0- o 0 o c o- o c o- o-- - ri Li G
u %D yy v~ =--= F %O 1- 'G F ~n M1 ti N 7 N ~D ? %D O M1 N G
L: > - .--. oo m v r C ...: V v6 oo v t-i oo v n ' -u N 10 n P 0, m r'1 F m m F m m t1 10 V m q - _ U
Gu y V
o v t2 O m'O rf V O+ e~7 U c vi -.. v~ ? N ~O r~ N N P O
u O ~D f~1 N o0 ~D ~= ==== C m t- G1 V1 00 00 C~ N \O Q O+ C C~ '/~ vi G
> N ? Q N N N ~ F m G1 m 00 N f+l 10 F m F f'1 a m S O U u F-r. o .Z b N f~1 F f~9 VY N N N N V1 N v1 F CO N '~=~ ~' 0 V1 vl vl ~ 10 Q Y1 N ~O ~O ~O V ~ ~ V Vi ~ P1 Q 4 ~ N P
~Z o U 3 o ~
N n~O Q~ F p r ~ N~O N n~D N vi t~ ~n O O~ m ~p ~p ? --~ a ~ V O
ao p+ oc C C U O~ - O O T O~ C, O O m oC O, Q, O" ~O ap U = 5 u N N ... _ r. ~ - - C ~ _ ... ... - - _ ._ -u = O
c E ~
U (-~ u . ~ ~~+ ~u (_) I C Q .= O
O 0 O O O O O O O O O O O O O O O O O O O O O O ~ ~ _~
v-N I O O 00 O O v+ cG O N oC O o0 E c-I v v v a I r~ c c Q v v n c c v.-i v c v v v v v v'~ U-= ~
~ - ~
,LV. I I 7 ~

a..
= c =
~ U U
U o U ~ ~ V (7 Q U u LL
p 0 a V u e o e ~ ~
N U
U Z q N ~o U

= 3 4 As the results of Table I 1 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 compounds 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, HCI 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 HCI, a top liquid phase containing HF and a bottom liquid phase containing essentially acid free chiorofluorinated 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 and/or batch separation of HF and HCI from C-3 chlorofluorinated compounds.
This is desirous in any industrial halogenation reaction scheme or small scale reaction scheme because it is often necessary to remove HCI and HF from the reaction product. Typically, this is a costly endeavor, requiring the separate stripping of the HC! and subsequent distillation of the HF.

Example 16: Heterogeneous Phase Separation of C3C1F2_ The fluorination reaction of HF and C3CI2F6 comprised a reaction product stream containing approximately 40-45 weight % C3CIF7 and 50-55 wt % C3C12F6 on s~ _ . .
r =
WO 03/029173 PCT/L;S02130729 an acid free basis. The reaction product was cooled and sent directly to a 3.9 liter liquid phase separation tan]<. 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 HCI gas. The bottom liquid organic phase was decanted off to be pu.rified 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:
Table 12. Contents of Bottom Phase of Heterogenous Se aration %HF %HCI %Organic 1.5 2.5 96.0 --The top vapor phase gas stream contained primarily HC1 and was fed directly to a distillation column for simple distillation. The pressure was controlled for the entire system via this distillation pressure controller to distill HCI out the top. The HF phase composition is shown below in Table 13:
Table 13. Contents of Top Liquid Phase of Hetero2enous Se aration %HF %HCl %Organic 89.24 4.20 6.56 As Table 12 and 13 demonstrate, HF, HC1 and organic fluorination reaction products can be efficiently separated in a one-step process. This process is extremely useful because it negates the high costs associated w'ith 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 oreanic 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 III reaction products which include CFC-217ba. Accordingly, the halogenated orzanic compounds are premixed with hvdrogen and contacted with a metal containing catalyst at sufficient temperature to produce a hydrodehalogenation reaction product. In still another embodiment the hvdrodehalogenation reaction products include HFC-227ea. A reaction of this embodiment is shown below:
C3CIF7 + H? --- HFC-227ea + HCI
A sli2ht molar excess of H~ can be used if desirable but is not necessary. The H,:haloaenated organic compound molar ratio is in the range of about 0.2:1 to about 10:1, opti mal l y about 1.22:1 _ Referring now to Fig. 6, the hydrodehalogenation is performed in fixed bed reactor 4? containino 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 ferric chloride (FeC13) 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 ran2e 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 w-hether the catalysts are supported or not. However, supports w-hich are unreactive to halocarbons, HF, and oxy~en at hydrogenation temperatures up to hiQher such as metal fluondes, carbon. and titanium, may be used.
Referrin',- now to Fis. 7, the hi2h cost of noble metals led to concerns re2ardinQ
catalyst lifetime. Initial testin2 demonstrated that the catakst is somewhat fragile with acti~'itv dropping off within 5 davs. Fortunately, it has been discovered that the addition of a small amount of %~ ater to the reaction stream extended catakst lifetime.
The addition of water allows the catalyst to perfor-m in excess of 15 days.

Replacement sheet 37, Under Article 34 t 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 embodiment, 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 (C3CIF7 --> 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 I S 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.

' - . - - j-~;

= Table 14 Hvdrogqnation of iCIf, to HFC-227ea with Differcnt Metal and atal u rts tilctal Support Additivc Contact H2/ Temp. % Results - HFC=227ca Catalyst Time(s) C3CIF7 (C) Loading Conversion Selectivi 5% Pd Activatcd 16.6 1.5 150 5.8 67.5 Carbon 180 16.4 69.5 1"/s Pd CActivat arboo 19.1 2 150 12.2 83.6 180 47.9 89.8 200 78.8 91.2 225 96.8 87.6 D 250 99.8 87.0 i Activated f 1"/ Pd Carbon 36.7 1.8 150 26.7 83.5 f 180 67.3 90.2 c 200 72.0 90.0 r 225 92.8 87.1 e Activated n 0.5"/o Pd Carbon 15.4 1 150 3.1 74.4 t 180 5.8 66.9 S 200 9.6 75.8 Activated u 0.5% Pd Carbon 20.3 2.1 250 45.8 90.2 p 275 68.7 88.2 p 300 85.5 86.1 0 325 95.5 80.0 r 2.0"/o Cu/ Activated 18.6 2 150 13.4 86.4 s 0 6% Pd Carbon 180 50.8 89.3 L 200 74.8 87.9 225 87.6 83.7 a 250 97.7 80.7 d 2.0"/o Cu/ Activated 37 1.8 180 42.7 87.8 i 0.6% Pd Carbon n 200 67.5 85.4 225 83.4 85.9 250 98.3 83.4 2.0"/o Cu/ Activated 10.2 2.4 150 7.1 46.8 0.6'/e Pd Carbon 180 15.3 67.5 200 28 2 76.9 225 54.0 78.5 250 80.0 77.9 275 95.0 75.9 Different 0.5% Ru Alumina 22.4 1.3 150 2.5 22.4 Metals I80 4.0 32.5 200 5.0 39.4 0.5% Rh Alumina 23.6 1.5 ISO 12.9 67.1 180 26.0 77.5 200 26.6 83.6 0.5'/e Pt Aluniina 23.1 1.5 150 2,8 44.5 180 6 1 50.8 200 14.3 80.3 Additivcs 0 5% Pd Alumina H~% 21.9 1.4 180 63 1 98.1 0.5% Pd Alumina Hg ~ 21.9 1.4 180 73.8 97.2 0.5% Pd Alumina none 22. I 1.4 180 59.5 96.9 0.5% Pd # 1310 - Alumina none 21 1.4 180 96 6 95.7 r~ . ..
= WO 03/029173 PCT/1IS02/30729 As Table 14 demonstrates, the selectivity of the present invention is substantially the same when performed at less than optimum temperature parameters.
This allows for the selective production of selected isomers.
Table 15 and Fig. 7 demonstrate the catalyst life extension effectiveness of the present invention at varying levels of water addition. All conversions represented in Table 15 were performed at 180 C with a H, to C3CIF7 molar ratio between 0.9-1.5:1, a contact time of 20-30 seconds over a 0.5% Pd on Al catalyst.
Table 15. Catalvst Life Extension RUN TIivfE % %
450 ppm H20 (days) CONVERSION SELECTIVITY
C3C1F7 HFC-227ea 0.1 94.90 97.31 0.2 93.87 97.31 0.3 84.70 97.13 0.96 80.90 97.92 1.03 79.94 99.35 1.05 79.98 96.91 RUN TIiv1E % %
450ppm H20 (days) CONVERSION SELECTIVITY
C3C1F7 HFC-227ea 0.1 93.67 95.61 0.7 96.63 96.00 0.8 95.53 95.79 1.1 90.69 97.30 1.7 78.82 97.15 2.1 81.26 97.72 3.0 49.15 93.84 4.1 44.07 78.73 RUN TIiViE % %
0.29% H20 (days) CON VERSION SELECTIVITY
C3CIF7 HFC-227ea 0.1 95.81 96.09 0.3 98.40 93.54 1.2 98.36 96.40 1.3 98.40 96.44 1.3 98.31 96.26 1.3 96.58 96.13 4.1 96.53 96.30 4.2 95.88 95.76 4.3 95.87 95.89 4.3 95.77 95.74 5.0 96.48 95.78 - 5.1 94.84 95.79 5.2 92.59 95.36 5.3 91.89 97.39 6.2 89.60 97.32 6.3 91.18 97.44 6.3 90.91 98.14 7.0 85.48 97.10 7.1 83.84 97.22 7.3 79.20 97.20 7.3 77.89 97.13 8.0 69.32 97.10 8.2 71.62 97.04 8.3 76.70 97.17 8.3 80.16 97.50 11.0 60.41 96.61 11.0 58.41 96.41 11.2 56.68 96.36 11.9 57.05 96.40 12.1 55.97 96.35 12.3 55.96 96.33 12.9 54.04 96.22 12.9 54.30 96.22 RUN TLV1E % %
0.8% H20 (days) CONVERSION SELECTIVITY
C3CIF7 HFC-227ea 0.0 90.10 94.47 0.7 93.60 95.35 0.8 94.19 95.81 1.0 92.39 95.65 1.9 99.60 96.96 2.0 96.71 96.59 4.7 99.73 96.00 4.8 98.96 97.89 5.0 97.93 96.00 5.0 98.16 96.10 5.8 98.27 96.08 6.0 97.96 95.95 6.9 96.76 95.64 7_8 90.03 94.96 8.7 96.52 95.42 9.0 94.70 95.20 11.7 97.19 97.90 12.0 93.80 97.45 12.8 91.60 97.51 13.0 91.49 97.48 14.0 96.78 96.04 15.0 95.11 95.83 15.1 94.57 94.96 To demonstrate the increased catalyst life utilizing water in the dehydrohalogenation reaction according to this invention, catalyst, H2 and were prepared as described above with the addition of water as demonstrated in Table f WO 03/029173 PCTn'S02/30729 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 I, 11 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 II
(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.

WO 0.3/I)29173 = PCT/US02/30729 N a C ~ N~rN
V~~
u p C,) N r~ ;~ u, O O O N v~ ~O
y O ry ~p U C C O O O O C O O
u _ N O~ ery P O 00 N G1 Q 1~ N h m ~ r"+ oo O~ - N O
C..I N O N 00 ~O f~t N M1 v~ (:. V N
cUi e n ~-z - ~
r N f~ t~ Pry N t'1 ~O
\ = Vrv0 fn o U OO.oon~v~
r,~ O O r= ~O q .
r;, ~ UMm ~ U o 60 > U vvi v~i a rr ~ In a*
F~~ , N e~1 b Q"'~\ O fQ~1 u N Uc~mr~~Cv ", N f UO~mr ooQ~-.N~===
rU U~ d ao U=o n _.
C/) = ~ u 1 __ = N ~p p~
V ..J N u O O=.~ e~. t~ aC
V p e~f ~ O ri C U c v~ eu ~ O~
EoN to !e No N r U tn n~ o a !0 q ~
,N/=~ ' !~~_ c o ' v, C v C N N=~ O u L"" _ a \ =s ~~ U U ua C a n ~~==~ ~ d '~ u ~+. ~- u O u u U O O N vi ~O . 4~C O O 7 > mO - --~ (241 ~
C) ~(~U p Q u om U e-i vm o N U ooo~r'='v ooo=1 N o o c 0 c ;n U~. .~ ~. N n Vl h Vt N
N 1~ -= v1 Nm N fV m 2 1 L U Q V=f N N
C f L"' r Q. f'1 N['~
A S=. =~ EO C' !~ U
pO' ~ ~"~ -[L N LL CL. N f, U Vl Q QI-.r vf ~n zi.QC'~v7 t~~ L' 0000 J
O' h: U N O O O C O
~ =1 U
tl c fV N v~ r'1 u 0 C.~ -~D Q f=t 'J ~ N No, r O
O
= - n ~ U!'r - ~ i (=, t~ f'1 Q V1 t'1 u 4 V U O o "~ C: ~ O~ vVi N-s :/1 (~ N N ~ ' _ > U "
c c m >_;-t e '=
O.C O u p, eC e O
O u u r ~
p C~ 'Li _-= U Q R~n ~:"~ j= V
p ry ~r. R N
C
n xl U$ v t-4 A_ m E 1< U a E U C v'__ e N f~t V
V a 00 m pLL o u X 'u m X y O~ O u E
E
a:. E oQ Z
ory- LJ1U U~ r <' U U s UI= U O O
~o - =

. . _ ~

WO 03/029173 PCT/L'S02/30729 To demonstrate the separation of HFC-227 isomers, a standard distillation apparatus was utilized and configured according to the parameters shown in Tables 17 and 18 below. As indicated, Table 17 demonstrates distillation with a chlorofluorocarbon and Table 18 demonstrates distillation without a chlorofluorocarbon.

Table 17. Distillation with C3CIF7 Column Conditions Temperature ( C) I Take Off min) Pressure Overhead Bonom I Feed (gJmin) Overhead Bottoni Reflux Ratio si 61.8 294 36 2.93 2.21 0.45 25 Se aration Results-GC Profiles HFC- FC-218 HFC- HCFC- HFC- HFC- Un{:nown CFC- CFC-134a 227ca 124 227ea 236fa 217ba 217ca Feed 0.00258 0.00987 I 0.07504 1 0.01 33.33046 0.159881 0.11694 16.11326 0.14152 Overhead 0.00295 0.00392 0.01543 i nd 99.97741 nd nd 0.00573 nd Take Off Bottom nd nd 0.12677 ~ 0 01923 57.10056 0.45827 0.30565 41.63464 0.35488 Take Off nd = not detected Ratio HFC-227e3/HFC-227ca Feed 1 l 10 Ovcrhead 6458 Bottom 450 Isomer Reduction Ratio Overhead/Feed) 5.8 Table 18. Distillation without C3CIF.7 Column Conditions Temperature ( C) I Take Off rJmin Pressure Ovenccad Bottom Feed (,-/min) Ovencc3d Bonom Reflux Ratio Siq) 45.5 21.8 22.~ 3.59: 3461 0.45 23 Sc aration Results-CC Profiles HFC- FC-218 1 HFC- HCFC-124 HFC- HFC- Unknown 1 CFC- CFC-134a 227ca 227ea 236fa 2t7ba 217ca Feed 0 C0296 1 00687 1 0.0271 nd 99.95139 nd nd 0.00928 nd Overhead 0.00328 0.00671 0 01 195 nd 1 99.98003 nd nd nd - nd Take Off Bottom nd nd 0 07773 nd 99.86733 nd nd 0.0549 nd Take Ofr nd not detected Ratio HFC-227ca/HFC-227ca Feed 3688 Overhead 8367 Bonom 1285 Isomer Reduction Ratio Ovcnccadj'Fr_d) 2.3 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 mi.xture 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-217ca. Other isomer mixtures that can be purified according to the present invention Nr-ill be apparent to those skilled in the art.

In accordance with the present invention, chlorofluorinated 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 found 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.

ExamRle 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 96:1,.
This mixture was heated in the presence of a pre fluorinated Chrom-gel (provided by Englehard) catalyst at various temperatures outlined below with the results shown in Table 19 below.
Table 19. Selective Destruction of CFC-216ba Isomer Reaction Relative Ratio Temperature( C) of CFC-216aa:CFC-216ba 325 257:1 250 325.03:1 250 309.53:1 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.

WO 03/029173 PCT![:S02/30719 To demonstrate still another embodiment of the present invention, non-limiting example 21 is provided.

Examole 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 8 1:
1.
This mixture was heated in the presence of a pre-fluorinated Chrom-gelm catalyst at various temperatures outlined below with the results shown in Table 20 below.

Table 20. Selective Destruction of CFC-217ca Isomer Reaction Relative Ratio Temperature( C) of C FC-2 l 7ba: C FC-217ca 250 252.79:1 280 548.11:1 As can easily be seen from Table 20, the process according to the presenf 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 kzeping 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 Cl2 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. Hvdrohalogenated compounds suited for selective halogenation according to this invention will be obvious to trose 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 r ~ . , 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 ClZ 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 Haloa,enation 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. --WO 03/029173 PCT/US02:30729 _ Q M
~ N O :J O C
Uy, O O O C
U N N N P~' N n O N U
LL.
U G O O O C O O C

a q r (i ~ N c:s N
N ~ V-~ O O O
N N 7 7 7~O oo O C ~y O O O O
U
L O'OO O O 0 O O 0 U O O O ~L O O O O p =
00 'O N f~
U O 06 00 eC
t; v~ oo vi O O~ Ol P C~
U 00 O~ r P N N N N U
u oo eo ~C t~ ~C oo =~G V2 cn a o% a a a a r o~
CC

ao o e~
v j ~ C . ? 7 O~ N r1 0o H
0 r v'r, v o o 00 n c ~ U

CC r v~
o e n (j Q o eo 0 ~ ~ N
T
6) '~' o 0o c b c~ ~- v~', U
N -' - N - N 0 O
a>
~ N
õ E
,==+ c ~ r, ao m :.
u - ~
co c~ O~ rv~ vi oo U
Ey U ~ ~ ~ N -N t'1 N

U
o ~ L2 O
E O O
O O

o c o U u U
p C u o u u ~ v ~ o o~ n o~ O o a a N - r-Ni rNi tNi r ~N ~ C-1 G

U
b c e - -'uC~O o ~ O ~
4 o A q U
:_. U u a 00 N N U 00 N N ~
~ N N C~ N N a0 .
U U =- =
LL. U U. Q "o U V U

As Table 21 demonstrates, the present invention can be used to even funher reduce the content of the undesired isomer. It is contemplated that once reduced the more isomerically pure reaction product can be recycled or further refined.

Replacenlent sheet 52, Under Article 34

Claims (44)

1. A hydrogenation process comprising contacting a compound with a catalyst in the presence of water to form a hydrogenated compound.

2. The process of claim 1 wherein the contacting further comprises contacting the compound with H2.

3. The process of claim 1 wherein a ratio of the H2 to the compound is from 0.2:1 to 10:1.

4. The process of claims 2 or 3 wherein a ratio of the H2 to the compound is at least about 1.2:1.

5. The process of claims 2 or 3 wherein the water is from about 0.04 to about 12 percent by weight of the compound.

6. The process of claims 2 or 3 wherein the water is at least about 0.8 percent by weight of the compound.

7. The process of claims 2 or 3 wherein the catalyst contains a metal.

8. The process of claims 2 or 3 wherein the catalyst comprises palladium and a catalyst support.

9. The process of claims 2 or 3 wherein the compound comprises C3F7Cl and the hydrogenated compound comprises C3F7H.

10. A process for purifying CF3CFHCF3 comprising distilling a mixture comprising CF3CFHCF3, CF3CF2CF2H, and at least one chlorofluorocarbon to form a solution comprising CF3CFHCF3.

11. The process of claim 10 wherein the at least one chlorofluorocarbon comprises C3ClF7.

12. The process of claim 11 wherein the mixture comprises a mole ratio of the chlorofluorocarbon to the CF3CFHCF3 of from about 0.1 to about 10.

13. The process of claim 11 wherein the mixture comprises a mole ratio of the chlorofluorocarbon to the CF3CFHCF3 of at least about 1:2.

14. A process for purifying chlorofluorinated compounds comprising:
providing a reaction product comprising HCl, HF, and a C-3 chlorofluorinated compound;
phase separating the reaction product into a gas phase comprising the HCl, a top liquid phase comprising the HF, and a bottom liquid phase comprising the C-3 chlorofluorinated compound; and removing the bottom liquid phase to form a solution comprising the C-3 chlorofluorinated compound.

15. The process of claim 14 wherein the C-3 chlorofluorinated compound comprises C3F7Cl.

16. The process of claim 15 wherein the phase separating comprises altering the reaction product temperature to a temperature of from about 20°C to about 75°C.

17. The process of claim 16 wherein the temperature is about 25°C.

18. A process for purifying reaction products comprising:
providing a reaction product comprising HF and at least one C-3 chlorofluorinated compound;
phase separating the reaction product into a top liquid phase comprising HF and a bottom liquid phase comprising the at least one C-3 chlorofluorinated compound;
and physically separating the top and bottom phases to form a solution comprising the at least one C-3 chlorofluorinated compound.

19. The process of claim 18 wherein the C-3 chlorofluorinated compound comprises a C-3 chlorofluorinated compound having at least six fluorine atoms.

20. The process of claim 19 wherein the phase separating comprises altering the reaction product temperature to a temperature of from about -30°C
to about -10°C.

21. The process of claim 20 wherein the temperature is about -20°C.

22. A process for separating chlorofluorinated compounds comprising:
providing a first solution comprising both first and second C-3 chlorofluorinated compounds, the first compound having at least six fluorine atoms and the second compound having less than six fluorine atoms;
preparing a mixture comprising the first solution and water;
phase separating the mixture into at least three phases; a gas phase comprising the first compound, an upper liquid phase comprising the water, and a lower liquid phase comprising the second compound; and removing the gas phase from the upper and lower liquid phases to form a second solution comprising the first compound.

23. The process of claim 22 wherein the mixture further comprises a basic compound.

24. The process of claims 22 or 23 wherein the basic compound comprises KOH.

25. The process of claims 22 or 23 wherein the first compound comprises C3F6C12 and the second compound comprises C3F5C13.

26. The process of claims 22 or 23 wherein the first compound comprises C3F6C12, and the second compound comprises C3F5Cl3 the phase separating comprises altering the first solution reaction temperature to a temperature of from about 25°C to about 75°C.

27. The process of claims 22 or 23 wherein the first compound comprises C3F6Cl2 and the second compound comprises C3F5Cl3 the phase separating comprises altering the first solution reaction temperature to a temperature of about 50°C.

28. A process for purifying chlorofluorinated compounds comprising:
providing a first mixture comprising both first and second isomers of a C-3 chlorofluorinated compound, the first mixture having a first ratio of the first isomer to the second isomer; and contacting the mixture with a catalyst to form a second mixture comprising a second ratio of the first isomer to the second isomer, wherein the first ratio is less than the second ratio.

29. The process of claim 28 wherein the contacting further comprises heating the mixture to a temperature of from about 250°C to about 350°C.

30: The process of claim 28 wherein wherein the contacting further comprises heating the mixture to a temperature of about 280°C

31. The process of claim 28 further comprising separating at least a portion of the first isomer from the second mixture wherein the separating comprises distilling the second mixture to form a solution comprising the portion of the first isomer.

32. The process of any one of claims 28 to 31 wherein the C-3 chlorofluorinated compound comprises C3F6Cl2, the first isomer comprises CF3CCl2CF3, and the second isomer comprises CF3CClFCF2Cl.

33. The process of any one of claims 28 to 31 wherein the C-3 chlorofluorinated compound-comprises C3F7Cl, the first isomer comprises CF3CClFCF3, and the second isomer comprises CF3CF2CF2Cl.

34. The process of any one of claims 28 to 31 wherein the catalyst comprises chromium.

35. A process for halogenating compounds comprising:
providing a first mixture comprising both first and second isomers of a hydrofluorinated compound, the first mixture having a first ratio of the first isomer to the second isomer; and contacting the mixture with a halogenating agent to form a second mixture having a second ratio of the first isomer to the second isomer, the first ratio being less than the second ratio.

36. The process of claim 35 further comprising separating at least a portion of the first isomer from the second mixture wherein the separating comprises distilling the second mixture to form a solution comprising the portion of the first isomer.

37. The process of claim 35 further comprising contacting the mixture with the halogenating agent in the presence of a catalyst.

38. The process of any one of claims 35 to 37 wherein the hydrofluorinated compound comprises C3F7H, the first isomer comprises CF3CFHCF3, and the second isomer comprises CF3CF2CF2H.

39. The process of any one of claims 35 to 37 wherein the contacting comprises heating the mixture to a temperature of from about 200°C to about 350°C.

40. The process of any one of claims 35 to 37 wherein the contacting comprises heating the mixture to a temperature of at least about 300°C.

41. The process of any one of claims 35 to 37 wherein the halogenating agent comprises Cl2.

42. The process of any one of claims 35 to 37 wherein the halogenating agent comprises Cl2 and a molar ratio of the Cl2 to the mixture is from about 0.16:1 to about 3:1.

43. The process of any one of claims 35 to 37 wherein the halogenating agent comprises Cl2 and a molar ratio of the Cl2 to the mixture is at least about 2.5:1.

44. The process of claims 36 or 37 wherein the catalyst comprises activated carbon.