| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 08.01 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 14.08.01 |
| PATENT TITLE |
Catalysts for halogenated hydrocarbon processing and their preparation and use |
| PATENT ABSTRACT |
A process is disclosed for changing the fluorine content of halogenated hydrocarbons containing from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The process involves producing the catalyst by heating a single phase solid catalyst precursor having the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 (where x is in the range of 0.1 to 1 and M is at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In) to about 400.degree. or less to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride. Also disclosed are multiphase catalyst compositions consisting essentially of chromium fluoride and a crystalline fluoride of at least one metal selected from the above group (provided the atom percent of Cr is at least equal to the atom percent of the crystalline fluoride metals). Phases of the crystalline fluorides are homogeneously dispersed with phases of the chromium fluoride. Preparation of homogeneously dispersed multiphase catalyst compositions consisting essentially of fluorides of chromium and crystalline fluorides of at least one other metal selected from the above group (the atom percent Cr being at least equal to the atom percent of the other metal(s)) is also disclosed. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 09.07.96 |
| PATENT REFERENCES CITED |
L.E. Manzer and V.N.M. Rao, Catalytic Synthesis of Chlorofluorocarbon Alternatives, Advances in Catalysis, 39, 329-350, 1993. Karl Wieghardt, Hans Siebert, Schwingungsspektren under Kristallgitter von Hexamminchrom(III)-und Hexamminkobalt(III)-Hexafluorometallaten(III), Journal of Molecular Structure, 7, 305-313, 1971. D.-H.Menz and B. Ehrhardt, Study of the Thermal Behaviour of [Cr(NH3)6]MF6(M=Cr,A1,Fe,Ga and In) and [Cr(NH3)6]F3 HF H20, Journal of Thermal Analysis, 42, 925-935, 1994. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. A method of preparing a homogeneously dispersed multiphase catalyst composition consisting essentially of fluorides of chromium and at least one other metal selected from the group consisting of Al, Sc, V, Fe, Ga and In wherein the atom percent of Cr is at least equal to the atom percent of said at least one other metal, characterized by: heating a single phase solid catalyst precursor composition of the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 where M is at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In and x is in the range of 0.1 to 1 to a temperature sufficient to remove essentially all of the nitrogen-containing component of said formula composition to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride. 2. A multiphase catalyst composition prepared in accordance with the process of claim 1. 3. A multiphase catalyst composition consisting essentially of chromium fluoride and a crystalline fluoride of at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In, provided that the atom percent of Cr is at least equal to the atom percent of said crystalline fluoride metals, wherein phases of said crystalline fluorides are homogeneously dispersed with phases of said chromium fluoride. 4. A process for increasing the fluorine content of a saturated or olefinic compound having the formula C.sub.n H.sub.a F.sub.b X.sub.c where n is an integer from 1 to 6, a is an integer from 0 to 12, b is an integer from 0 to 13, c is an integer from 1 to 13, and each X is independently selected from Cl and Br, in the presence of a multiphase catalyst, characterized by: producing said catalyst by heating a single phase solid catalyst precursor having the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 wherein x is in the range of 0.1 to 1 and M is at least one metal element selected from the group consisting of Al, SC, V, Fe, Ga and In, to about 400.degree. C. or less to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride; and reacting said saturated or olefinic compound with HF in the vapor phase in the presence of said catalyst. 5. The process of claim 4 wherein M is Al and x is about 1. 6. The method of claim 1 wherein the nitrogen-containing compound of the single phase solid catalyst precursor decomposes at about 400.degree. C. or less; and wherein the single phase solid catalyst precursor is heated to about 400.degree. C. or less to produce the multiphase composition. 7. The method of claim 6 wherein the single phase solid catalyst precursor is (NH.sub.3).sub.6 CrAlF.sub.6. 8. A multiphase catalyst composition prepared in accordance with the method of claim 6. 9. The multiphase catalyst composition of claim 3 consisting essentially of chromium fluoride and a crystalline fluoride of Al. 10. A process for increasing the fluorine content of a saturated or olefinic compound having the formula C.sub.n H.sub.a F.sub.b X.sub.c where n is an integer from 1 to 6, a is an integer from 0 to 12, b is an integer from 0 to 13, c is an integer from 1 to 13, and each X is independently selected from Cl and Br, in the presence of a multiphase catalyst, characterized by: reacting said saturated or olefinic compound with HF in the vapor phase in the presence of the multiphase catalyst composition of claim 2, claim 3, claim 8, or claim 9. 11. A process for changing the fluorine content of a halogenated hydrocarbon compound having the formula C.sub.p H.sub.g F.sub.h Cl .sub.j where p is an integer from 1 to 2, g is an integer from 1 to 3, h is an integer from 1 to 4, and j is an integer from 1 to 3, in the presence of a multiphase catalyst, characterized by: conducting a disproportionation of said compound in the presence of the multiphase catalyst composition of claim 2, claim 3, claim 8 or claim 9. 12. A process for increasing the fluorine content of a saturated or olefinic compound having the formula C.sub.n H.sub.a F.sub.b X.sub.c where n is an integer from 1 to 6, a is an integer from 0 to 12, b is an integer from 0 to 13, c is an integer from 1 to 13, and each X is independently selected from Cl and Br, in the presence of a multiphase catalyst, characterized by: producing said multiphase catalyst by the method of claim 1, claim 6 or claim 7; and reacting said saturated or olefinic compound with HF in the vapor phase in the presence of the catalyst produced by said method. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION This invention relates to fluoride compositions, and their preparation and use, and more particularly to chromium and aluminum fluoride catalysts and preparation and use of such catalysts for processing halogenated hydrocarbons. BACKGROUND Numerous processes have been developed for changing the fluorine content of halogenated hydrocarbons using chromium containing catalysts. These include increasing the amount of fluorine of halogenated hydrocarbons which are not fully fluorinated, decreasing the fluorine content of halogenated hydrocarbons containing fluorine, and redistributing the number of fluorine atoms among two or more hydrocarbon molecules which are not fully fluorinated. Various catalysts have been proposed for use in facilitating processes such as hydrofluorination, hydrochlorination (i.e., fluorine substitution by chlorine) and disproportionation which involve halogenated hydrocarbons. See, e.g., L. E. Manzer et al., Adv. Catal. 39, pp. 329-350 (1993). A well known class of art catalysts includes chromium supported on alumina, fluorinated alumina or aluminum fluoride. Typically these materials are prepared by depositing a soluble salt of chromium on an alumina or aluminum fluoride support. While this method does produce a combination catalyst, the support material and the material deposited thereon are not uniformly mixed. Techniques such as coprecipitation which rely upon physical characteristics of individual components (e.g., solubility) also typically yield non-homogeneously dispersed products due to differences in physical and chemical properties of the components. There is an interest in developing means for a more homogeneous dispersion of chromium on an aluminum fluoride support which can be used as a catalyst for changing the fluorine content of halogenated hydrocarbons. SUMMARY OF THE INVENTION This invention provides a process for changing the fluorine content of halogenated hydrocarbons containing from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The process is characterized by producing said catalyst by heating a single phase solid catalyst precursor having the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 where x is in the range of 0.1 to 1 and M is at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In, to about 400.degree. C. or less to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride. This invention also provides multiphase catalyst compositions consisting essentially of chromium fluoride and a crystalline fluoride of at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In, provided the atom percent of Cr is at least equal to the atom percent of said crystalline fluoride metals, wherein phases of said crystalline fluorides are homogeneously dispersed with phases of said chromium fluoride. A homogeneously dispersed multiphase catalyst composition consisting essentially of fluorides of chromium and crystalline fluorides of at least one other metal selected from the group consisting of Al, Sc, V, Fe, Ga and In wherein the atom percent Cr is at least equal to the atom percent of said at least one other metal may be prepared in accordance with this invention by heating a corresponding single phase solid catalyst precursor composition of the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 wherein M and x are as defined above, to a temperature sufficient to remove essentially all the nitrogen-containing component of said formula composition to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride. DETAILED DESCRIPTION The catalytic process of this invention for changing the fluorine content of halogenated hydrocarbons containing from 1 to 6 carbon atoms employs a multiphase catalyst prepared in a manner which provided homogeneous dispersion of multiple metal components by converting a decomposable single phase solid catalyst precursor to a multiple phase catalyst. A single phase catalyst precursor of the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 may be prepared by conventional synthetic techniques (e.g., crystallization). Normally, the ratio of the metal components, (2-x):(x), should be between 19:1 and 1:1. Of particular note are compositions where the ratio of Cr to M (e.g., Al) in the precursors is about 1:1 (i.e., x is about 1). It will be evident that providing single phase precursors as described arranges the two components, Cr and M, in a structured arrangement where Cr and M are closely connected through the NH.sub.3 and F components. As a result of the arrangement of the components in the precursor, when the single phase structure collapses upon heating, uniformly interspersed phases of Cr and M are formed. These are referred to herein as "homogeneously dispersed" phases. It is desirable to convert the single phase precursor to multiphase composition at a moderately elevated temperature (e.g., about 400.degree. C. or less). While some single phase structures are unstable and collapse upon heating, this conversion is ordinarily accomplished by decomposing the decomposable nitrogen-containing component of the composition. Accordingly, the decomposable nitrogen-containing component preferably decomposes at about 400.degree. C. or less. The catalysts used for changing the fluorine content of halogenated hydrocarbons should contain fluoride. When the multiphase composition is produced by heating the single phase precursor in air or other oxygen-containing atmosphere (e.g., O.sub.2) oxyfluorides and/or oxides may be present. These may be at least partially converted to fluoride by contacting the multiphase composition with a vaporizable fluorine-containing fluorinating compound. Typically, where additional fluoride is desired, a multiphase composition is treated with a vaporizable fluorine-containing fluorinating compound such as HF, SF.sub.4, COF.sub.2, CCl.sub.3 F, CCl.sub.2 F.sub.2, CHF.sub.3 or CCl.sub.2 FCClF.sub.2, at elevated temperatures (e.g., at about 200.degree. C. to about 450.degree. C.) until the desired degree of fluorination is obtained (see, e.g., U.S. Pat. No. 4,902,838). Included in this invention is a process for increasing the fluorine content of a saturated or olefinic compound having the formula C.sub.n H.sub.a F.sub.b X.sub.c, wherein n is 1 to 6, a is 0 to 12, b is 0 to 13 and c is 1 to 13, and where each X is independently selected from Cl and Br, by reacting the saturated compounds with HF in the vapor phase. The present invention also provides a process for the disproportionation of a compound having the formula C.sub.p H.sub.g F.sub.h Cl.sub.j, where p is an integer from 1 to 2, g is an integer from 0 to 3, h is an integer from 1 to 4 and j is an integer from 1 to 3. These processes are respectively characterized by reacting the C.sub.n H.sub.a F.sub.b X.sub.c compound with HF and conducting the disproportionation of the C.sub.p H.sub.g F.sub.h Cl compound, in the presence of a mutiphase catalyst containing fluorine, which has a phase containing chromium fluoride homogeneously dispersed with a phase containing a fluoride of a metal selected from the group consisting of Al, Sc, V, Fe, Ga, In and mixtures thereof. The mutiphase catalyst containing fluorine can be prepared by heating a corresponding single phase fluoride composition of the formula (NH.sub.3).sub.6 Cr.sub.2-x M.sub.x F.sub.6 wherein M and x are as defined above, to a temperature sufficient to remove all the nitrogen-containing component of the composition. A more active catalyst may often be achieved by contacting the multiphase composition with a vaporizable fluorine-containing fluorinating compound. Typically, the multiphase composition can be treated with a vaporizable fluorine-containing fluorinating compound such as HF, SF.sub.4, COF.sub.2, CCl.sub.3 F, CCl.sub.2 F.sub.2, CHF.sub.3 or CCl.sub.2 FCClF.sub.2, at elevated temperatures (e.g., at about 200.degree. C. to about 450.degree. C.). Nevertheless this treatment is not essential. In one embodiment a homogeneously dispersed multiphase composition consisting of chromium fluoride and beta-AlF.sub.3 is prepared from (NH.sub.3).sub.6 CrAlF.sub.6 a known compound (K. Wieghardt et al., J. Mol. Struc., 7, 305-313 (1971)) by heating at about 350.degree. C. to about 400.degree. C. for a suitable period (typically one hour or more), preferably in air. Essentially all the nitrogen-containing component will be decomposed. The reaction of said compounds of the formula C.sub.n H.sub.a F.sub.b X.sub.c with HF in the presence of the catalyst of the instant invention is conducted at about 150.degree. C. to 500.degree. C., preferably for saturated compounds at about 175.degree. C. to 400.degree. C., and more preferably for saturated compounds at about 200.degree. C. to about 350.degree. C., with a contact time of about 1 to about 120 seconds, preferably about 5 to about 60 seconds. The amount of HF should be at least a stoichiometric amount. Typically, the molar ratio of HF to the said compounds of the formula C.sub.n H.sub.a F.sub.b X.sub.c can range from about 1:1 to about 100:1, preferably about 2:1 to 50:1, and more preferably about 3:1 to 10:1. In general, with a given catalyst composition, the higher the temperature and the longer the contact time, the greater is the conversion to fluorinated products. The above variables can be balanced, one against the other, so that the formation of higher fluorine substituted products is maximized. Examples of olefinic compounds which may be reacted with HF include CHCl.dbd.CCl.sub.2, CCl.sub.2.dbd.CCl.sub.2, CCl.sub.3 CCl.dbd.CClCCl.sub.3, CH.sub.2.dbd.CCl.sub.2, CCl.sub.2.dbd.CClCCl.sub.3, CHF.dbd.CF.sub.2, CH.sub.2.dbd.CF.sub.2 and CClF.dbd.CF.sub.2. Of note is a catalytic process for producing 2-chloro-1,1,1-trifluoroethane (HCFC-133a) by the fluorination of a trihaloethene of the formula CX.sub.2.dbd.CHCl wherein each X is chlorine or fluorine. Starting materials include trichloroethene, 1,2-dichlorofluoroethene and 1-chloro-2,2-difluoroethene. Trichloroethene is preferred. HCFC-133a is produced by reacting the above unsaturated compounds with HF in the vapor phase in the presence of the catalyst of this invention. The reaction of the above trihaloethenes with HF in the presence of the catalyst of the instant invention is conducted at about 150.degree. C. to 350.degree. C., more preferably about 175.degree. C. to 250.degree. C. Oxygen may be added, if desired. Also of note is a catalytic process for producing 2,2-dichloro-1,1,1-trifluoroethane (CHCl.sub.2 CF.sub.3, i.e., HCFC-123), 1,1,1,2-tetrafluorochloroethane (CHClFCF.sub.3, i.e., HCFC-124) and pentafluoroethane (CHF.sub.2 CF.sub.3, i.e., HFC-125) by the fluorination of a tetrahaloethene of the formula C.sub.2 Cl.sub.4-y F.sub.y, wherein y equals 0 to 3. Starting materials include CCl.sub.2.dbd.CCl.sub.2, CClF.dbd.CCl.sub.2, CClF.dbd.CClF CF.sub.2.dbd.CCl.sub.2, and CF.sub.2.dbd.CClF. Tetrachloroethene is preferred. HCFC-123, HCFC-124 and/or HFC-125 is produced by reacting the above unsaturated compounds with HF in the vapor phase in the presence of the catalyst of this invention. Examples of saturated compounds which may be reacted with HF include CH.sub.2 Cl.sub.2, CHCl.sub.3, C.sub.2 Cl.sub.6, C.sub.2 H.sub.4 Cl.sub.2, C.sub.2 Cl.sub.5 F, C.sub.2 Cl.sub.4 F.sub.2, C.sub.2 Cl.sub.3 F.sub.3, C.sub.2 Cl.sub.2 F.sub.4, C.sub.2 ClF.sub.5, C.sub.2 HCl.sub.5, C.sub.2 HCl.sub.4 F, C.sub.2 HCl.sub.3 F.sub.2, C.sub.2 HCl.sub.2 F.sub.3, C.sub.2 HClF.sub.4 and CCl.sub.3 CH.sub.2 CCl.sub.3. Of note are catalytic processes for reacting 1,1,1-trichloro-1,1,1-trifluoroethane (CCl.sub.3 CF.sub.3, i.e., CFC-113a), or reacting dichloromethane, with HF, in the vapor phase in the presence of the catalyst of this invention. For the reaction of CFC-113a with HF to yield CCl.sub.2 FCF.sub.3 (CFC-114a), the HF:CCl.sub.3 CF.sub.3 ratio can vary widely. The HF:113a ratio should be at least stoichiometric but preferably can vary from about 2:1 to about 10:1. For the reaction of dichloromethane to yield difluoromethane (CH.sub.2 F.sub.2, HFC-32), the molar ratio of HF to CH.sub.2 Cl.sub.2 preferred ranges from about 1:1 to about 10:1. The reaction temperature normally ranges from about 180.degree. C. to about 375.degree. C. (e.g., from about 200.degree. C. to about 350.degree. C.) The homogeneously dispersed chromium fluoride and beta aluminum fluoride catalyst may be used in accordance with this invention in a catalytic process for the disproportionation of hydrochlorofluorocarbons of the formula, C.sub.p H.sub.g F.sub.h Cl.sub.j having from 1 to 2 carbon atoms, at least one hydrogen and at least one fluorine, to produce hydrofluorocarbons. Suitable halofluorocarbons for disproportionation include CH.sub.2 ClF, CH.sub.3 CClF.sub.2, CCl.sub.2 FCClF.sub.2 and CHClFCF.sub.3. The products of the disproportionation reactions are respectively, CH.sub.2 F.sub.2 and CH.sub.2 Cl.sub.2, CH.sub.3 CF.sub.3 and CH.sub.2.dbd.CCl.sub.2, C.sub.2 Cl.sub.4 F.sub.2 and C.sub.2 Cl.sub.2 F.sub.4, and CHCl.sub.2 CF.sub.3 and CHF.sub.2 CF.sub.3. In certain embodiments substantial isomerization can occur. Reactions for changing the fluorine content of a halogenated hydrocarbon (e.g., the reaction of compounds of the formula C.sub.n H.sub.a F.sub.b X.sub.c with HF and the disproportionation of compounds of the formula C.sub.p H.sub.g F.sub.h Cl.sub.j) may be conducted in any suitable reactor, including fixed and fluidized bed reactors. The reaction vessel should be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride and hydrogen chloride such as Inconel.TM. nickel alloy and Hastelloy.TM. nickel alloy. The reaction products may be separated by conventional techniques, such as distillation. It is noted that many halogenated hydrocarbon products of the above reactions form azeotropes with HF, HCl or other halogenated hydrocarbons. Some of the reaction products will have desired properties for commercial use. For example CCl.sub.3 CF.sub.3 (CFC-113a) can be used to prepare CFC-114a which can then be converted to CH.sub.2 FCF.sub.3 (HFC-134a) by hydro-dechlorination. Others, such as CCl.sub.2.dbd.CCl.sub.2 can be recycled back to reactors which are being used for the synthesis of halofluorocarbons. Pressure is not critical. Atmospheric and super-atmospheric pressures are the most convenient and are therefore preferred. Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and does not constrain the remainder of the disclosure in any way whatsoever. |
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