PROCESS FOR PRODUCTION OF 1,1,1-TRIFLUORO-2,2-DICHLOROETHANE

Abstract: A process for production of 1,1,1-trifluoro-2,2-­ dichloroethane which process comprising reacting 1,1,1-­ trifluoro-2-chloroethane with hydrogen chloride and oxygen in the presence of a metal salt as a catalyst.

Description: The present invention relates to a process for production of 1,1,1-trifluoro-2,2-dichloroethane. Particularly, the present invention relates to a process for 1,1,1-trifluoro-2,2-dichloroethane comprising reacting 1,1,1-trifluoro-2-chloroethane with hydrogen chloride and oxygen in the presence of a metal salt as a catalyst. Description of the Related Art 1,1,1-Trifluoro-2,2-dichloroethane is expected to replace trichlorofluoromethane, since it does not decompose ozone in the stratosphere. Then, it is desired to develop an economical process for the production of 1,1,1-trifluoro-2,2-dichloroethane. Several processes for the production of 1,1,1-trifluoro-2,2-dichloroethane have been already proposed. For example, Czechoslovakian Patent No. 136,735 and Japanese Patent Kokai Publication No. 222038/1983 describe a process comprising reduction of 1,1,1-trifluoro-2,2,2-trichloroethane. Japanese Patent Publication No. 27375/1986 describes a process comprising isomerization of 1,1,2-trifluoro-1,2-dichloroethane. U.S. Patent No. 3,755,477 describes a process comprising fluorination of ethylene tetrachloride. Japanese Patent Kokai Publication No. 82711/1978 describes a process comprising photo chlorination of 1,1,1-trifluoro-2-chloroethane. However, from the point of view of the economical production, the above known processes for the production of 1,1,1-trifluoro-2,2-dichloroethane are not necessarily suitable since yield and selectivity through such the process are not high enough. SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a commercially advantageous process for the production of 1,1,1-trifluoro-2,2-dichloroethane with overcoming the problems described above. According to the present invention, there is provided a process for the production of 1,1,1-trifluoro-2,2-dichloroethane which process comprises reacting 1,1,1-trifluoro-2-chloroethane with hydrogen chloride and oxygen in the presence of a metal salt as a catalyst. With the process of the present invention, it is possible to produce 1,1,1-trifluoro-2,2-dichloroethane economically and commercially. DETAILED DESCRIPTION OF THE INVENTION 1,1,1-Trifluoro-2-chloroethane, as a starting material of the present process, can be easily produced by fluorination of trichloroethylene with anhydrous hydrogen fluoride in a liquid or gas phase. The metal salt used as the catalyst in the present process includes a metal halide, for example NiCl₂, CuCl₂, FeCl₂ and so on. Also, the combination of such the metal halide with KCl provides good results. It is preferred to use the metal salt carried on a support, for example, made of a metal oxide such as aluminum oxide or a metal fluoride such as aluminum fluoride. The amount of the catalyst carried on the support is suitably selected depending on the reaction conditions, the desired conversion and so on. Generally, the molar ratio of the metal salt as the catalyst to the metal oxide as the support is in the range of from 0.005 to 2, particularly from 0.01 to 1.0, for example 0.01. In the process of the present invention, it is most preferable to use CuCl₂ supported on the support made of aluminum fluoride. Generally, any size of the support can be used, and it is most preferable to use a spherical support or a pellet form support of which size is in the range of from 1 to 10 mm, particularly from 2 to 4 mm. The the amounts of 1,1,1-trifluoro-2-chloroethane, hydrogen chloride and oxygen to be supplied to a reactor is preferably controlled so that the amount of hydrogen chloride is more than 0.1 mole, for example 0.5 mole and the amount of oxygen is from 0.05 to 0.5 mole, for example 0.2 mole per mole of 1,1,1-trifluoro-2-chloroethane, respectively. In addition to this, the reaction is preferably carried out at the molar ratio of oxygen to hydrogen chloride of less than 1, for example at 0.5. The purity of oxygen is not necessarily 100 %, and the oxygen diluted with an inert gas such as nitrogen can be also used in the present process. Commercially, it is advantage to use air from the point of economical view. The reaction temperature is preferably in the range of from 250 to 550 °C, particularly from 350 to 500 °C. The present process is generally performed under the atmospheric pressure, although it can be performed under pressure. Further, it is also possible to carry out the reaction under diluting by an inert gas such as nitrogen. The contact time between the catalyst and the reactants can be suitably selected depending on the reaction conditions, especially the reaction temperature. Generally, the contact time is preferably controlled in the range of from 0.5 to 30 seconds. In the present process, any type of reactor, for example a tube reactor, can be used as long as good contact between the catalyst carried on the catalyst and the reactants is achieved. In the process of the present invention, the reactor such as the tube reactor filled with the catalyst is heated to a preselected temperature dependent on the reaction temperature, for example, in an electrical furnace. Then, the reactants (1,1,1-trifluoro-2-chloroethane, hydrogen chloride and oxygen) are supplied to the reactor to start the reaction. The exit gas from the reactor is generally collected after water washing and drying steps. In order to improve the conversion of 1,1,1-trifluoro-2-chloroethane, it is advantageous to recycle the unreacted 1,1,1-trifluoro-2-chloroethane to the reactor which is recovered from the top of a purification apparatus for purifying the produced gas. Present invention will be hereinafter explained further in detail by following examples. Example 1 A tube reactor made of Hastelloy C (20 mm in inner diameter, 400 mm in length) was filled with 50 ml of spherical support particles (from 2 to 4 mm in diameter) made of AlF₃ carrying NiCl₂ in the molar ratio of 0.01 to AlF₃ and heated to 500 °C in a nitrogen stream. After stopping the supply of nitrogen, 1,1,1-trifluoro-2-chloroethane, hydrogen chloride and oxygen are supplied to the reactor at the flow rate of 100 ml/min., 50 ml/min. and 25 ml/min (based on the standard condition), respectively. The contact time based on the average residence time was about 6 seconds. The exit gas from the tube reactor was collected after water washing and drying steps, and then analyzed with a gas chromatography. The conversion of 1,1,1-trifluoro-2-chloroethane was 48 % and the selectivity to 1,1,1-trifluoro-2,2-dichloroethane was 69 %. Examples 2 and 3 Example 1 was repeated except that the support made of AlF₃ carrying CuCl₂ in the molar ratio of 0.03 to AlF₃ was used as the catalyst and the reaction temperature was changed as shown in Table 1. The results are also shown in Table 1. Example 2 Example 3 Reaction temp. 400 °C 450 °C Conversion of 1,1,1-trifluoro-2-chloroethane 35 % 43 % Selectivity to 1,1,1-trifluoro-2,2-dichloroethane 79 % 72 % Examples 4-6 Example 2 was repeated except that the flow rates of the reactants supplied to the tube reactor were changed as shown in Table 2. The results are also shown in Table 2. Example 4 Example 5 Example 6 Flow rate of 1,1,1-trifluoro-2-chloroethane 100 ml/min. 100 ml/min. 100 ml/min. Flow rate of hydrogen chloride 25 ml/min. 25 ml/min. 100 ml/min. Flow rate of oxygen 5 ml/min. 25 ml/min. 25 ml/min. Contact time 9.4 sec. 8.1 sec. 5.4 sec. Conversion of 1,1,1-trifluoro-2-chloroethane 8 % 22 % 42 % Selectivity to 1,1,1-trifluoro-2,2-dichloroethane 89 % 82 % 73 %

Claims: A process for production of 1,1,1-trifluoro-2,2-dichloroethane which process comprising reacting 1,1,1-trifluoro-2-chloroethane with hydrogen chloride and oxygen in the presence of a metal salt as a catalyst. The process according to claim 1, in which said metal salt is selected from the group consisting of NiCl₂, CuCl₂ and FeCl₂. The process according to claim 1, in which said metal salt is carried on a support made of a material selected from the group consisting of a metal fluoride and a metal oxide.

Inventors: FURUTAKA, YASUHISA, HOMOTO, YUKIO, HONDA, TSUNETOSHI
Applicants: DAIKIN INDUSTRIES, LIMITED
Application year: 1989
Main classification: C07C19
IPC codes: C07C17, B01J27, C07B61, C07C19, C07C67