GAS-PHASE FLUORINATION PROCESS

Abstract: An improved gas-phase process for the manufacture of 1,1,1-trifluorodichloroethane and/or 1,1,1,2-tetrafluorochloroethane by contacting a suitable tetrahaloethylene with hydrogen fluoride in the presence of a selected metal in combination with a high fluorine content aluminum-containing compound, the reaction being conducted under controlled conditions whereby the production of pentafluoroethane is minimized.

Description: TITLE GAS-PHASE FLUORINATION PROCESS This application is a continuation-in-part of pending application Serial No. 07/070,826, filed July 7, 1987, titled 'Gas Phase Fluorination Process." FIELD OF THE INVENTION An improved process for the manufacture of 1,1,1-trifluorodichloroethane (FC-123) and/or 1,1,1,2-tetrafluorochloroethane (FC-124), more particularly, a gas-phase reaction of a suitable tetrahaloethylene with hydrogen fluoride in the presence of a selected metal in combination with a high fluorine content aluminum-containing compound, the reaction being conducted under controlled conditions whereby the production of pentafluoroethane is minimized. BACKGROUND OF THE INVENTION Canadian Patent No. 1,196,345 (1985) describes a process for the preparation of CF3CHXY (X = H, F; Y = H, F, Cl , Br f I) by addition of HF to the corresponding ethylene in the presence of chromium oxyfluoride at 20-200°C, expecially 60-180°C. U.S. 3,755,477 describes a process for producing fluoπ ' nated aliphatic hydrocarbons which comprises fluorinating a halogenated aliphatic hydrocarbon, including tetrachloroethylene and chlorotrifluoroethylene, by reaction in the gas phase with hydrogen fluoride in the presence of a steam-treated and calcined chromium oxide catalyst prepared by a multi-step process. Example 23, col. 5, shows tetrachloroethylene as a raw material with formation of CF3CHCI2 (20%), CF3CHCIF (20%), CF3CHF2 (30%), and CF3CCIF2 (20%) at 10/1 HF/C2CI4 mol ratio, 5.4 seconds contact time and 360°C reaction temperature. Example 24, col. 5, shows chlorotrifluoroethylene as a raw material with formation of CF2=CF2 (20%) and CF3CHCIF (13%) at 1.8/1 HF/C2CIF3 mol ratio, 4 seconds contact time and 320°C reaction temperature. In these examples, less desirable pentafluorinated products are obtained in a greater amount than the desired tri- and tetrafluoro products. U.S. 3,258,500 describes a process for the catalytic vapor phase reaction of HF with halohydrocarbons, including tetrachloroethylene including chlorotrifluoroethylene, employing a catalyst that consists essentially of a heat-activated anhydrous chromium (III) oxide which may be supported on alumina. This catalyst is highly active. Example 17, col. 14, shows fluorination of tetrachloroethylene with this catalyst, like that of the above '477 patent, produces large quantities of the less desirable highly fluorinated pentafluoroethane. At 400°C the product distribution is 35.0% pentafluoroethane, 9.2% l-chloro-l,2,2,2-tetrafluoroethane, and 3.5% l,l-dichloro-2,2,2-trifluoroethane. At 300°C the product distribution is 38.3% l-chloro-l,2,2,2-tetrafluoroethane, 25.4% pentafluoroethane, and 16.0% l,l-dichloro-2 r 2,2-trifluoroethane. Example 20, coT.15, shows chlorotrifluoroethylene yields CF3CHF2 as the major product at 400 β C. GB 1,000,485 describes a process for the preparation of organic fluorinated compounds by fluorination of halo-olefins in the gaseous phase and at a temperature preferably within the range 200°C to 400°C. The catalyst consists essentially of partially fluorinated alumina impregnated with one or more polyvalent metal halides. The polyvalent metal may be chromium, cobalt, nickel, or manganese. The total content of polyvalent metal halide expressed as oxide is not more than 15% by weight of the partially fluorinated (70-80%) alumina expressed as alumina. Example 4, (Table 4) shows reaction of tetrachloroethylene with HF over such catalyst yields CF3CHCI2 as the major product at 220-290°C. In addition, the patent states that if fluorination of the catalyst is excessive, the activity of the catalyst is impaired (page 3, column 2, lines 85-87). The references do not disclose how to produce selectively both 1,1,1-trifluorochloroethane and 1,1,1,2-tetrafluorochloroethane while minimizing the production of the pentafluoroethanes, especially at high tetrahaloethylene conversions. The process of the instant invention achieves the desired high degree of selectivity by minimizing the formation of the pentafluoroethane, through catalyst selection and control of the reaction variables as discussed below and illustrated in the Examples. SUMMARY OF THE INVENTION What has been discovered is a process for the preparation of 1,1,1-trifluorodichloroethane and/or 1,1, 1,2-tetrafluorochloroethane by fluorination of a tetrahaloethylene, C2Cl4-χF x , wherein x = 0 to 3, comprising contacting in the gaseous phase at about 275°C to about 450°C said tetrahaloethylene and HF with a catalyst comprising a metal in an oxidation state greater than zero, said metal selected from the group consisting of chromium, manganese, rhodium, nickel, cobalt and mixtures thereof, said metal in combination with an aluminum-containing compound consisting essentially of aluminum and fluorine in such proportions that the fluorine content corresponds to an AIF3 content of at least 90% by weight of the catalyst composition exclusive of the metal, said AIF3 content being obtained by pretreatment of the unfluorinated catalyst with a vaporizable fluorine-containing compound. DETAILS OF THE INVENTION The tetrahaloethylene of this invention is defined by the formula C Cl4- x F x , wherein x = 0 to 3, and includes CCl2=CCl2, CClF=CCl2, CC1F=CC1F, CF2=CCl2, and CF2=CC1F, and mixtures of these. Tetrachloroethylene is preferred. By a high fluorine content aluminum-containing compound is meant a composition comprising aluminum and fluorine in such proportions that the total fluorine content of the catalyst composition taken as A F3 corresponds to at least 90 weight percent, exclusive of the metal, i.e., chromium, manganese, rhodium, nickel and cobalt, preferably 95 weight percent AIF3 or more. The remainder of the aluminum-containing compound may include alumina or aluminum oxyfluoride. The high fluorine content aluminum-containing compound can be prepared in-situ by exhaustive fluorination of alumina impregnated with at least one chromium, manganese, rhodium, nickel or cobalt compound which may be in the form of the oxide, oxyhal de, halide or pseudohalide or such other form which is convertible to the fluoride or oxyfluoride under the conditions of the pretreatment step described herein. The halides include fluorides, chlorides, or bromides. The pseudohalides include cyanides, cyanates and thiocyanates. The preferred metals are manganese, rhodium, nickel and cobalt. The most preferred metal is cobalt. The total content of chromium, manganese, rhodium, nickel or cobalt expressed as the divalent oxide is not more than 20% by weight of the supported catalyst. The catalyst of the instant invention can be prepared prior to reaction with the tetrahaloethylene, by impregnating Al2θ3 with the desired metal compound and treatment with a fluorine-containing compound, suc as HF, SF4, CCI3F, CCIF2, CHF3 or CC12FCC1F2, at elevated temperatures until the desired degree of fluorination is obtained, e.g., at about 200 degrees Centigrade to about 450 degrees Centigrade. The treatment with HF or other vaporizable fluorine-containing compound can conveniently be done in the reactor which is to be used for contacting tetrachloroethylene with HF. By vaporizable fluorine-containing compound is meant a fluorine-containing compound which will convert the unfluorinated catalyst of the instant invention to the desired degree of fluorination using the pretreatment conditions described herein. A suitable catalyst may be prepared, for example, as follows: A quantity of AI2O3 is impregnated with a solution of a catalytically effective amount of one or more metal halides or pseudohalides of chromium, manganese, rhodium, nickel, or cobalt. By catalytically effective amount is meant an amount of the metal expressed as the divalent oxide between abou 0.02 to 20 weight percent of the alumina support, preferably 0.1 to 5 weight percent. The impregnated AI2O3 can be dried until essentially all moisture is removed, e.g., for about 18 hours at about 300°C. The dried catalyst is then transferred to the reactor to b used. The temperature is then gradually increased to about 400 β C while maintaining a flow of N2 through the reactor to remove any remaining traces of moisture from the catalyst and the reactor. The temperature is then lowered to about 200°C and HF diluted with N2 is passed through the reactor. The N2 can be gradually reduced until only HF is being passed through the reactor. At this point the temperature can be increased to about 450°C and held at that temperature to convert the impregnated AI2O3 to a fluoride content corresponding to at least 90% AIF3, e.g., for 15 to 300 minutes, depending on the HF flow and the catalyst volume. The reaction of the tetrahaloethylene with HF in the presence of the catalyst of the instant invention is conducted at 275°C to 450°C, preferably about 300 β C to 400 β C, and most preferably about 325°C to 350°C, with a contact time of about 5 to 100 seconds, preferably about 10 to 90 seconds, and most preferably about 15 to 60 seconds. The molar ratio of HF to the tetrahaloethylene can range from about 1/1 to 20/1, preferably about 3/1 to 10/1, and most preferably about 4/1 to 7/1. If desired, the process may be run at temperatures less than about 275°C but for a given HF/C2C14 ratio and contact time a decline in temperature results in a decrease in conversion of the C2C , a decrease in the production of CF3CHCI2 and CF3CHC1F, and an increase in the formation of the underfluorinated products such as C2HCI4F and C2C13F2- However, if the goal is to manufacture the under fluorinated products, the catalyst of this invention is well suited for this purpose when used at temperatures of less than about 275°C. In general, with a given catalyst composition, the higher the temperature, the greater the HF/tetrahaloethylene ol ratio, and the longer the contact time, the greater is the conversion of the tetrahaloethylene to fluorinated products. The above variables can be balanced, one against the other, so that formation of FC-123 is favored over FC-124 and the production of these two compounds taken together is maximized and that of higher fluorinated products minimized. A key feature of the invention is that through catalyst selection and process control, as described herein, the desired tri- and tetrafluoro products can be obtained as the major products at high tetrahaloethylene conversions, normally between about 30% and about 90%. Preferably, the reaction variables are controlled so as to keep the production of the pentafluoro product below about 10 area percent, as determined gas chomatographically, of the products produced. Thus, as illustrated in the examples with tetrachloroethylene, the tri- and tetrafluoro products are obtained in very high yields while minimizing the production of higher fluorinated products even at high conversions of tetrachloroethylene. Underfluorinated compounds formed during the course of the reaction, such as CHCI2CCIF2, CC1F=CC12, and CHCI2CCI2F, can be recycled to the reactor for the production of additional FC-123 and FC-124. In addition, FC-123 can be recycled to the reactor for the production of additional FC-124 when this is desired. The reaction of the tetrahaloethylene with HF 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 such as Hastelloy and Inconel. Pressure is not critical. Atmospheric and superatmospheric pressures are the most convenient and are therefore preferred. The fluorinated alkanes produced by the invention have utility as blowing agents and refrigerants. They can also be used as starting materials for the preparation of other useful compounds. For example, FC-124 can be used to prepare 1,1,1,2-tetraf1uoroethane. EXAMPLES In the following illustrative examples, all parts and percentages are by weight and all temperatures are Centigrade unless otherwise stated. All reactions used commercial HF containing only trace amounts of water. General Procedure for Fluorination The reactor (a 0.5 inch ID, 12 inch long Inconel pipe) was charged with the amount of unfluorinated catalyst as described in the following examples, and placed in a sand bath. The bath was gradually heated to 400° while nitrogen gas at a flow rate of 50 ml/minute was passed through the reactor to remove traces of water. The temperature was lowered to 200° and HF and nitrogen gas (1:4 molar ratio) were passed through the reactor and the nitrogen flow was decreased with time until neat HF was being passed through the reactor. At this point, the temperature was gradually raised to 450° and maintained there for 15 to 300 minutes. The fluorine content of the catalyst composition corresponded to an AlF3 content, exclusive of the metal, of at least 95%. The initial fluorine content of the catalyst composition can be determined to correspond to an ATF3 content, exclusive of the metal, of at least 90%. Thi determination is based on the following calculation related to this reaction: AI2O3 + 6 HF — > 2 A1F3 + 3 H O y = weight of unfluorinated catalyst' composition which has been dried at a temperature of at least 400° for at least four hours in a stream of dry nitrogen, air or other suitable inert medium, minus the weight o metal compound which is in the unfluorinated catalyst composition. z = weight of fluorinated catalyst composition minus the weight of metal compound calculated as metal fluoride. Let x = weight of AI2O3 remaining after fluorination y - x = weight of reacted AI2O3 z - x = weight of AIF3 in the fluorinated alumina (y - x)168/102 = z - x Weight of AIF3 as % of dry fluorinated alumina can then be calculated as follows: fz - x) 100% z The temperature was then decreased to the indicated values and, thereafter, CC1 =CC1 flow was started. The flows of HF and CC1 =CC12 we e adjusted to give the indicated molar ratios and contact times. diameter, column containing "Krytox" perfluorinated polyether on an inert support and a helium flow of 35 cc/minute. Gas chromatographic conditions were 70° for 3 minutes followed by temperature programming to 180° at a rate of 6°/minute. EXAMPLES 1 - 2 The General Procedure for Fluorination was followed using 19.8 g. (30 cc) of NiCl2/Al2θ3 (2% Ni) as the initial catalyst charge. The results of the reaction of HF with CCl2=CCl2 over the prepared catalyst are given in Table 1. TABLE 1 Example 1 2 Temp. β C 325 350 HF/C2C14 ( ol ratio) 5/1 6/1 Contact Time (sec.) 45 30 Conversion % 58.7 61.2 Area Percent CF3CHC12 70.0 60.6 CF3CHCIF 12.4 20.3 CF3CHF2 0.5 1.3 CF3CHC12 plus CF3CHC1F 82.4 80.9 The reactor effluent was scrubbed with aqueous potassium hydroxide to remove HC1 and HF and sampled on-line with a Hewlett Packard HP 5890 gas chromatograph using a 20 foot long, one-eighth inch diameter, column containing "Krytox" perfluor nated polyether on an inert support and a helium flow of 35 cc/minute. Gas chromatographic conditions were 70° fo 3 minutes followed by temperature programming to 180° at a rate of 6°/minute. EXAMPLES 3 - 4 The General Procedure for Fluorination was followed using 19.5 g. (30 cc) of MnCl2/Al2θ3 (1.87% Mn) as the initial catalyst charge. The results of the reaction of HF with CCl2=CU2 over the prepared catalyst are given in Table 2. TABLE 2 Example Temp. °C 350 375 HF/C2CI4 (mol ratio) 6/1 10/1 Contact Time (sec.) 30 25 Conversion % 70.4 61.5 Area Percent CF3CHC12 67.8 58.5 CF3CHC1F 18.5 17.6 CF3CHF2 1.0 1.1 CF3CHC12 plus CF3CHC1F 86.3 76.1 EXAMPLES 5 - 9 The General Procedure for Fluorination was followed using 18.4 g. (30 cc) of C0CI2/AI2O3 (2.0% Co) as the initial catalyst charge. The results of the reaction of HF with CCl2=CCl2 over the prepared catalyst are given in Table 3. TABLE 3 Example 5 6 7 5 9 Temp. °C 350 350 350 350 350 HF/C2CI4 (mol ratio) 7/1 10/1 5/1 5/1 3/1 Contact Time (sec.) 13.2 19.3 31.8 17.6 25.7 Conversion % 87.3 90.3 86.8 75.7 60.0 Area Percent CF3CHCI2 56.5 52.8 53.6 57.8 52.1 CF3CHCIF 37.2 41.1 39.4 32.2 32.9 CF3CHF2 1.6 2.1 2.2 1.5 2.5 CF3CHCI2 Plus CF3CHCIF 93.7 93.9 93.0 90.0 85.0 EXAMPLES 10 - 13 The General Procedure for Fluorination was followed using 20.4 g. (30 cc) of CrCl3/Al2θ3 (5.2% Cr) as the initial catalyst charge. The results of the reaction of HF with CC12=CC1 over the prepared catalyst are given in Table 4. TABLE 4 Example 10 11 12 13 Temp. β C 425 350 350 350 HF/C2CI4 (mol ratio) 4/1 4/1 5/1 6/1 Contact Time (sec.) 15 60 60 60 Conversion % 62.1 78.3 78.1 80.3 Area Percent CF3CHCI2 31.4 50.8 49.6 46.1 CF3CHC1F 22.2 28.5 29.7 33.3 CF3CHF2 9.8 6.9 7.3 7.2 CF3CHCl2 . plus CF3CHCIF 53.6 79.3 79.3 79.4 EXAMPLES 14 - 19 The General Procedure for Fluorination was followed using 20.4 g. (30 cc) of C0CI2/AI2O3 (2% Co) as the initial catalyst charge. The ratio of HF/C2C14 was 6/1 and the contact time was 30 seconds. The results of the reaction of HF with CCl2=CCl2 over the prepared catalyst are given in Table 5. TABLE 5 Example 14 15 16 17 18 19 Temp. °C 265 255 245 235 225 215 Conversion % 36.2 29.9 25.3 21.3 16.5 12.9 Area Percent CF3CHCI2 54.1 43.1 32.8 23.4 11.3 4.7 CF3CHCIF 1.1 1.0 0.4 0.0 0.0 0.0 CCIF2CHCI2 29.6 40.6 50.2 58.7 52.1 43.7 CCI2FCHCI2 0.6 0.7 1.2 1.9 1.9 2.3 Other 14.6 14.6 15.4 16.0 34.7 49.3

Claims: We Claim: 1. A process for the preparation of 1,1,1-trifluorodichloroethane and/or 1,1,1,2-tetrafluorochloroethane by fluorination of a tetrahaloethylene, C2Cl4- x F x , wherein x = 0 to 3, comprising contacting in the gaseous phase -at about 275°C to about 450°C said tetrahaloethylene and HF with a catalyst comprising at least one metal in an oxidation state greater than zero, said metal selected from the group consisting of chromium, manganese, rhodium, nickel, cobalt and mixtures thereof, said metal in combination with a high fluorine content aluminum-containing compound consisting essentially of aluminum and fluorine in such proportions that the fluorine content corresponds to an AIF3 content of at least 90% by weight of the catalyst exclusive of said metal, said AIF3 content being obtained by pretreatment of the unfluorinated catalyst with a vaporizable fluorine-containing compound. 2. The process of Claim 1 wherein the tetrahaloethylene is tetrachloroethylene. 3. The process of Claim 1 wherein the catalyst contains about 0.02 to about 20 weight percent of said metal expressed as the divalent oxide. 4. The process of Claim 1 wherein the catalyst contains about 0.1 to about 5 weight percent of said metal expressed as the divalent oxide. 5. The process as in Claims 1, 2, or 3 wherein the HF is contacted with the tetrahaloethylene at a mol ratio of about 1/1 to about 20/1, at a temperature of about 275°C to about 400°C, and a contact time of about 5 to about 100 seconds. 6. The process of Claim 4 wherein conversion of the tetrahaloethylene to fluorinated products is between about 30% and about 95%. 7. The process of Claim 1 wherein the said metal is selected from the group consisting of manganese, rhodium, nickel and cobalt. 8. The process of Claim 6 wherein the said metal is cobalt. 9. The process of Claim 4 wherein the product stream has a CF3CHCI2 content greater than that of CF3CHC1F, and the combined total of CF3CHCI2 and CF3CHCIF is greater than that of CF3CHF2 in the product stream. 10. The process of Claim 8 wherein the amount of the CF3CHF2 in the product stream is less than ten percent. 11. The process of Claim 1 further comprising the step of recycling at least a portion of the CF3CHCI2 produced to the contacting step for conversion to additional CF3CHCIF. 12. The process of Claim 1 wherein the vaporizable fluorine-containing compound is selected from the group consisting of HF, SF4, CCI3F, CC12F , CHF3 or CC12FCC13F2.

Inventors: MANZER LEO E, RAO V N MALLIKARJUNA, MANZER, LEO, E., RAO, V., N., MALLIKARJUNA
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1989
Main classification: C07C17
IPC codes: B01J27, C07B61, C07C17, C07C19