R22(디플루오르모노클로로메탄) 열분해반응에 의한 테트라플루오르에틸렌의 합성

김상채; 김철웅; 문상진; 소원욱; 김수진; 이정민

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.6, 1134-1140, December, 1995

Export Citation

R22(디플루오르모노클로로메탄) 열분해반응에 의한 테트라플루오르에틸렌의 합성

Pyrolysis of R22( Difluoromonochloromethane) for TFE(Tetrafluoroethylene) Synthesis ; Dry Process

김상채, 김철웅, 문상진, 소원욱, 김수진, 이정민

초록

Tetrafluoroethylene 제조를 위한 R22 열분해반응을 일반적인 상압유통식 반응기에서 반응온도(655∼770℃), 체류시간(0.05∼0.5초) 및 N₂/R22 물비(3.0∼7.0)를 변수로 수행하였다. 반응온도와 체류시간이 증가함에 따라 R22 전화율은 증가하였으나 TFE 선택도는 감소하였다. 희석제의 사용은 반응성의 향상을 가져왔으며 R22와의 혼합정도는 생성물의 조성에 큰 영향을 미치는 것으로 나타났다. 속도론으로부터 R22 열분해반응의 주반응은 CF₂ 생성반응으고 추정되었고 속도식은 다음과 같은 1차식으로 나타낼 수 있었다. kτ=-0.5·f_R22·X + (1+0.5·f_R22)ln1/1-x 이 때 속도상수(k)의 활성화에너지는 45.19-49.06kca1/mo1 범위로 계산되었다.

Pyrolysis of R22 for tetrafluoroethylene was carried out using the conventional atmospheric flow reactor. The range of reaction temperature, residence time and N₂/R22 molar ratio were 665∼770℃, 0.05∼0.6 sec, and 3.0∼7.0, respectively. With increasing reaction temperature and residence time, R22 conversion increased, but selectivity of TFE decreased. The use of diluent(N₂) resulted in enhancing the reactivity, and the degree of mixing R22 with N₂ affected the composition of produces clearly. The formation of CF₂ might be suggested as the key reaction for pyrolysis of R22 from kinetics experiment. The following first order equation fitted well with experimental results. kτ= - 0.5·f_R22·X+(1+0.5·f_R22)ln 1/1-X The range of activation energy for the rate constant was obtained between 45.19 kcal/mol and 49.86 kca1/mo1.

[References]

Kenneth SR, British Patent, 983,222 (1962)
Gozzo F, Ragazzini M, France Patent, 1,369,777 (1964)
Du Pont De Nemours EI, British Patent, 911,215 (1962)
Charles AB, U.S. Patent, 2,615,925 (1952)
Allied Chemical Co., Netherland Patent, 6,411,278 (1963)
Haruo S, Makoto H, Br. Patent, 1,041,738 (1966)
Du Pont De Nemours EI, European Patent, 0,371,747 (1990)
Park JD, Benning AF, Downing FB, Lancius JF, McHarness RC, Ind. Eng. Chem., 39, 354 (1947)
Chinoy PB, Sunavala PD, Ind. Eng. Chem. Res., 26, 1340 (1987)
Edwards JW, Small PA, Ind. Eng. Chem. Fundam., 4, 397 (1965)
Makoto H, Nippon Kag. Kaishi, 10, 1406 (1978)
Venkateswarln Y, Murti PS, Chem. Process. Eng., Oct., 25 (1970)
Broyer E, Bekker AY, Ritter AB, Ind. Eng. Chem. Res., 27, 208 (1988)
DeCorso SM, Mumford S, Carrubba RV, Heck R, ASME Paper No. 76-GT-4, 159 (1977)
Norton FJ, Refrig. Eng., 65, 62 (1957)
Gozzo F, Patrick CR, Nature, 202, 1329 (1964)
Panshin YA, Russ. J. Phys. Chem., 40, 1197 (1966)
Barnes GR, Cox RA, Simmons RF, J. Chem. Soc., 1176 (1976)
Reid RC, Prausnitz JM, Poling BE, "The Properties of Gases & Liquids," 4th ed., 658, McGraw-Hill, New York (1986)

[Referenced By]

[1] Kenneth SR, British Patent, 983,222 (1962)

[2] Gozzo F, Ragazzini M, France Patent, 1,369,777 (1964)

[3] Du Pont De Nemours EI, British Patent, 911,215 (1962)

[4] Charles AB, U.S. Patent, 2,615,925 (1952)

[5] Allied Chemical Co., Netherland Patent, 6,411,278 (1963)

[6] Haruo S, Makoto H, Br. Patent, 1,041,738 (1966)

[7] Du Pont De Nemours EI, European Patent, 0,371,747 (1990)

[8] Park JD, Benning AF, Downing FB, Lancius JF, McHarness RC, Ind. Eng. Chem., 39, 354 (1947)

[9] Chinoy PB, Sunavala PD, Ind. Eng. Chem. Res., 26, 1340 (1987)

[10] Edwards JW, Small PA, Ind. Eng. Chem. Fundam., 4, 397 (1965)

[11] Makoto H, Nippon Kag. Kaishi, 10, 1406 (1978)

[12] Venkateswarln Y, Murti PS, Chem. Process. Eng., Oct., 25 (1970)

[13] Broyer E, Bekker AY, Ritter AB, Ind. Eng. Chem. Res., 27, 208 (1988)

[14] DeCorso SM, Mumford S, Carrubba RV, Heck R, ASME Paper No. 76-GT-4, 159 (1977)

[15] Norton FJ, Refrig. Eng., 65, 62 (1957)

[16] Gozzo F, Patrick CR, Nature, 202, 1329 (1964)

[17] Panshin YA, Russ. J. Phys. Chem., 40, 1197 (1966)

[18] Barnes GR, Cox RA, Simmons RF, J. Chem. Soc., 1176 (1976)

[19] Reid RC, Prausnitz JM, Poling BE, "The Properties of Gases & Liquids," 4th ed., 658, McGraw-Hill, New York (1986)