Process for preparing chlorotrifluoroethylene

Abstract: Chlorotrifluoroethylene is prepared by reacting tetrafluoroethylene with hydrogen chloride in the presence of a metallic catalyst in a high yield without using 1,1,2-trichlorotrifluoroethylene which destroys the ozone layer.

Description: Field of the Invention The present invention relates to a process for preparing chlorotrifluoroethylene (hereinafter referred to as "CTFE") which is one of commercially important monomers. Description of the Related Art Hitherto, various methods for preparing CTFE have been disclosed in prior arts. For example, Japanese Patent Publication Nos. 5207/1982 and 5208/1982 disclose a liquid phase process comprising dechlorinating 1,1,2-trichlorotrifluoroethane (hereinafter referred to as "R-113") using zinc in an organic solvent, and Japanese Patent Publication No. 46049/1988 discloses a process for preparing CTFE comprising reacting R-113 and hydrogen in a gas phase in the presence of a catalyst to effect dechlorination. In the dechlorination process using zinc, expensive zinc should be used and post-treatment of zinc chloride which is by-produced in a large amount is troublesome. The hydrogenation-dechlorination process has a drawback that the catalyst life is short. In addition, both processes use, as a starting material, R-113 the production of which will be banned in view of its ozone destruction property. As processes for preparing CTFE using no R-113, there are known co-pyrolysis of chlorodifluoromethane and dichlorodifluoromethane (Japanese Patent Publication No. 2132/1965) and a catalytic halogen-exchange process of tetrafluoroethylene and dichlorodifluoroethylene (hereinafter referred to as "R-1112") in the presence of a catalyst (Japanese Patent Kokai Publication No. 26239/1987). But, in the former process, the yield is low and purification of CTFE is difficult. In the latter process, R-1112 is expensive and the yield is low. SUMMARY OF THE INVENTION An object of the present invention is to provide a process for preparing CTFE in a high yield without using R-113 which destroys the ozone layer. According to the present invention, there is provided a process for preparing CTFE comprising reacting tetrafluoroethylene (hereinafter referred to as "TFE") with hydrogen chloride in the presence of a metallic catalyst. The reaction in the process of the present invention may be expressed by the reaction formula: CF 2 =CF 2 + HCl → CF 2 =CFCl + HF DETAILED DESCRIPTION OF THE INVENTION In the process of the present invention, the reaction temperature is usually from 100 to 500°C, preferably from 150 to 350°C. When the reaction temperature is lower than 100°C, the conversion of TFE is low. When the reaction temperature is higher than 400°C, amounts of byproducts such as the dimer of TFE increase unpreferably. In view of heat resistance of the catalyst and prevention of deterioration of catalytic activity, a more preferred reaction temperature range is 330°C or lower. Reaction pressure is usually from 9.81 kPa to 9.81 MPa (0.1 to 100 kg/cm 2 G), preferably around 9.81 10 4 Pa (1 kg/cm 2 G). The molar ratio of TFE to hydrogen chloride is from 0.1:1 to 10:1, preferably from 1:1 to 7:1, more preferably from 3:1 to 5:1. When the amount of TFE is too small, the byproducts such as dichlorodifluoroethylene generate in a larger amount. When the amount of TFE is too large, the conversion of TFE is low. The contact time is usually from 1 to 120 seconds, preferably from 15 to 60 seconds. The catalyst to be used according to the present invention is at least one metallic catalyst selected from the group consisting of an oxide of chromium, a halide of chromium, chromium oxyfluoride, an oxide of aluminum and a halide of aluminum. The catalyst may be used as such or supported on a carrier such as alumina, silica, activated carbon or titania. The unsupported chromium oxide catalyst is particularly preferred, since it increases the conversion of TFE so that productivity is increased. The catalyst can be produced by a per se conventional method. Before use, the chromium oxide catalyst may be activated with at least one halogen-containing compound having at least one fluorine atom such as TFE or hydrogen fluoride. The activation of the catalyst is carried out by flowing the halogen-containing compound over the catalyst placed in a reaction tube at a comparatively high temperature, for example, about 200 to 400°C for 1 minute to 1 hour. Together with the above halogen-containing compound, hydrogen chloride may be used. By such activation, chromium oxide is fluorinated to give chromium oxyfluoride: CrO x F y ( 0.5 x + y = 3, 0 < x < 1.5, 0 < y < 3 ), and carbon is deposited on the surface of the catalyst. Thereby, the catalyst is poisoned against the formation of the by-products, and the conversion of TFE decreases while a selectivity of CTFE increases. An amount of carbon for poisoning the catalyst is preferably from 0.5 to 10 % by weight based on the weight of Cr 2 O 3 . When the amount of carbon is smaller than 0.5 % by weight, the selectivity of CTFE decreases. When it is larger than 10 % by weight, the conversion of TFE decreases. To prevent excessive deposition of carbon on the catalyst and decrease of the conversion of TFE, it is desirable to carry out the reaction at a temperature lower than the activation temperature of the catalyst. As the reaction proceeds, the catalyst is gradually poisoned, so that the conversion of TFE gradually decreases while the selectivity of CTFE increases. When the catalyst is excessively poisoned and the conversion of TFE greatly decreases, the catalyst is regenerated by heating it in air at a temperature of 200 to 300°C. PREFERRED EMBODIMENTS OF THE INVENTION The present invention will be explained in detail by the following Examples. Example 1 Using a pelletizer, chromium hydroxide powder was molded to form cylindrical pellets each having a diameter of 3 mm and a height of 3 mm. Cylindrical chromium hydroxide pellets (30 ml) were charged in a stainless steel reactor tube (a diameter of 1.91 cm (3/4 inch) and a length of 50 cm) and heated by an electric annular furnace at 350°C with flowing nitrogen through the tube to obtain a chromium oxide catalyst. After poisoning the catalyst by flowing TFE at a flow rate of 45 ml/min. for 30 minutes, TFE and hydrogen chloride were flowed over the catalyst in the tube at flow rates shown in Table 1. The composition of the produced gas was analyzed by gas chromatography. The reaction conditions and the composition of the produced gas after 4 hours from the start of the reaction are shown in Table 1. The results in the parentheses are those after 24 hours from the start of the reaction. In Table 1, R-125, R-115, R-124 and R-114 represent pentafluoroethane, chloropentafluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane and 1,2-dichlorotetrafluoroethane, respectively. Temp. (°C) Flow rate (ml/min.) TFE conversion (%) Selectivity (%) TFE HCl CTFE R-125 R-115 R-124 R-114 R-1112 350 45 45 52 53 2 12 6 5 17 310 45 45 37 51 8 7 9 5 12 300 90 30 24(8) 58(78) 6(0) 12(3) 8(4) 0(4) 11(5) 300 120 30 16(8) 71(79) 2(1) 7(5) 5(5) 1(2) 9(7) 250 45 45 33(17) 58(70) 6(4) 4(2) 9(6) 2(2) 15(12) Example 2 Activated alumina having a particle size of 2 to 4 mm (30 ml) on which 4 % by weight of CrCl 3 was supported was charged in a stainless steel reactor tube (a diameter of 1.91 cm (3/4 inch) and a length of 50 cm) and heated and well dried by an electric annular furnace at 350°C. Over this catalyst in the tube, TFE and hydrogen chloride were flowed at flow rates shown in Table 2. The composition of the produced gas was analyzed by gas chromatography. The reaction conditions and the composition of the produced gas after 2 hours from the start of the reaction are shown in Table 2. Temp. (°C) Flow rate (ml/min.) TFE conversion (%) CTFE selectivity (%) TFE HCl 300 12 12 11 76 350 12 12 27 74 400 25 25 53 55 400 45 45 45 59 Example 3 Silica gel having a particle size of 2 to 4 mm (30 ml) on which 14 % by weight of CrCl 3 was supported was charged in a stainless steel reactor tube (a diameter of 1.91 cm (3/4 inch) and a length of 50 cm) and heated and well dried by an electric annular furnace at 350°C. Over this catalyst in the tube, TFE and hydrogen chloride were flowed at flow rates shown in Table 3. The composition of the produced gas was analyzed by gas chromatography. The reaction conditions and the composition of the produced gas after 2 hours from the start of the reaction are shown in Table 3. Temp. (°C) Flow rate (ml/min.) TFE conversion (%) CTFE selectivity (%) TFE HCl 300 17 12 6 75 350 17 12 32 70 400 17 12 67 54 400 45 45 39 67 Example 4 Titanium oxide having a particle size of 2 to 4 mm (30 ml) on which 3 % by weight of CrCl 3 was supported was charged in a stainless steel reactor tube (a diameter of 1.91 cm (3/4 inch) and a length of 50 cm) and heated and well dried by an electric annular furnace at 350°C. Over this catalyst in the tube, TFE and hydrogen chloride were flowed at flow rates shown in Table 4. The composition of the produced gas was analyzed by gas chromatography. The reaction conditions and the composition of the produced gas after 2 hours from the start of the reaction are shown in Table 4. Temp. (°C) Flow rate (ml/min.) TFE conversion (%) CTFE selectivity (%) TFE HCl 350 17 17 48 47 400 45 45 55 42 Example 5 Using a pelletizer, chromium hydroxide powder was molded to form cylindrical pellets each having a diameter of 3 mm and a height of 3 mm. Cylindrical chromium hydroxide pellets (30 ml) were charged in a stainless steel reactor tube (a diameter of 1.91 cm (3/4 inch) and a length of 50 cm) and heated by an electric annular furnace at 350°C with flowing nitrogen through the tube to obtain a chromium oxide catalyst. By fluorinating the catalyst by flowing anhydrous hydrogen fluoride at a temperature of 200 to 300°C for 2 hours, a chromium oxyfluoride catalyst was prepared. Then, TFE and hydrogen chloride were flowed over this catalyst in the tube at flow rates shown in Table 5. The composition of the produced gas was analyzed by gas chromatography. The reaction conditions and the composition of the produced gas after one hour from the start of the reaction are shown in Table 5. Temp. (°C) Flow rate (ml/min.) TFE conversion (%) CTFE selectivity (%) TFE HCl 350 100 100 16 65 350 25 20 30 57 300 10 10 20 61 Example 6 In a stainless steel reactor reactor tube, 30 ml of activated alumina having a particle size of 2 to 4 mm was filled and heated with an annular electric heater. Over the alumina catalyst, TFE and hydrogen chloride were flowed to react them. The composition of the produced gas was analyzed by gas chromatography. The reaction conditions and the composition of the produced gas after 2 hours from the start of the reaction are shown in Table 6. Temp. (°C) Flow rate (ml/min.) TFE conversion (%) CTFE selectivity (%) TFE HCl 400 70 240 1 30 500 50 150 19 16

Claims: A process for preparing chlorotrifluoroethylene comprising reacting tetrafluoroethylene with hydrogen chloride in the presence of at least one metallic catalyst selected from the group consisting of an oxide of chromium, a halide of chromium, chromium oxyfluoride, an oxide of aluminum and a halide of aluminum. The process according to claim 1, wherein the reaction temperature is from 100 to 400°C. The process according to claim 1, wherein the reaction pressure is from 9.81kPa to 9.81 MPa (0.1 to 100 kg/cm 2 G). The process according to claim 1, wherein the contact time is from 1 to 120 seconds. The process according to claim 1, wherein the molar ratio of tetrafluoroethylene to hydrogen chluoride is from 0.1:1 to 10:1. The process according to claim 1, wherein said catalyst is a chromium catalyst. The process according to claim 6, wherein said chromium catalyst comprises Cr 2 O 3 . The process according to claim 6, wherein said chromium catalyst comprises chromium oxyfluoride of the formula: CrO x F y ( 0.5x + y = 3, 0 < x < 5, 0 < y < 3 ). The process according to claim 6, wherein said chromium catalyst is poisoned with carbon in an amount of 0.5 to 10 % by weight based on the weight of the chromium catalyst. The process according to claim 1, wherein said catalyst is supported on a carrier selected from the group consisting of alumina, silica, activated carbon and titania.

Inventors: NAKAGAWA KOUTAROU, OTSUKA TATSUYA, YAMAGUCHI FUMIHIKO, NAKAGAWA, KOUTAROU, OTSUKA,TATSUYA, YAMAGUCHI, FUMIHIKO, NAKAGAWA, KOUTAROU, YODOGAWA WORKS, OTSUKA,TATSUYA, YODOGAWA WORKS, YAMAGUCHI, FUMIHIKO, YODOGAWA WORKS
Applicants: DAIKIN IND LTD, DAIKIN INDUSTRIES, LIMITED
Application year: 1992
Main classification: C07C17
IPC codes: C07B61, B01J23, C07C17, C07C21