염소 라디칼이 촉매로 작용하는 에틸렌 디클로라이드 열분해 반응의 해석

이주혁; 최병석; 이상욱; 오주석; 이종협; Joohyouk Yi; Byung-Seok Choi; Sang-wook Lee; Joo Seok Oh; Jongheop Yi

HWAHAK KONGHAK, Vol.38, No.2, 296-303, April, 2000

Export Citation

염소 라디칼이 촉매로 작용하는 에틸렌 디클로라이드 열분해 반응의 해석

Analysis of Cl-Radical Catalysis in Ethylene Dichloride Pyrolysis Reaction

이주혁, 최병석, 이상욱¹, 오주석¹, 이종협 ^†

서울대학교 응용화학부
¹한화석유화학(주) 중앙연구소

Joohyouk Yi, Byung-Seok Choi, Sang-wook Lee¹, Joo Seok Oh¹, and Jongheop Yi^†

School of Chemical Engineering, Seoul National University, Korea
¹Research Center, Hanwha Chemical Corp., Korea

E-mail:

초록

본 연구에서는 무산소 조건의 Ethylene Dichloride(EDC) 열분해 공정을 화학 반응 속도론 기법을 이용하여 해석하고 그 결과를 현재 조업중인 실제 EDC 열분해 공정 결과와 비교 분석하였다. 200여개의 radical 연쇄 반응으로 이루어지는 EDC 열분해 반응 네트워크를 H 및 Cl abstraction, 열분해로 인한 radical 생성 및 소멸 이론에 따라 분류하여 전체 반응 네트워크를 체계적으로 구성하였으며, 그 결과를 바탕으로 조업 온도와 첨가제의 변화에 따른 EDC 분해 효율과 부산물 산출비율에 관한 상관 관계를 도출하였다. 본 연구를 통하여 상용 EDC 분해로의 해석 기법을 확립하게 되었으며, vinyl chloride의 수율 향상 방법 및 부산물 생성 메커니즘을 확립하여 EDC 분해로의 최적 조업 조건을 도출하는 방법론을 제시하였다.

The pyrolysis of ethylene dichloride(EDC) is investigated on the base of kinetic mechanism schemes. Hundreds of radicals and molecular reactions and H and Cl abstraction are involved and thermodynamic functions and reversible kinetics were considered simultaneously in the schemes. The cracking depth of EDC and the amount of by-products are calculated as a function of operating temperature and additive concentration. The calculated results are in good agreement with the trend of the commercial plant data. Suggested methodology can provide practical responses involved in the operation of an industrial EDC pylorysis unit.

Keywords:EDC;Ethylene Dichloride;Pyrolysis;Vinyl Chloride;Computational Chemical Kinetics

[References]

Moon SH, "Petrochemical Engineering," Seoul National University (1997)
Kurtz BE, Ind. Eng. Chem. Proc. Des. Dev., 11, 332 (1972)
Benson SW, Int. J. Chem. Kinet., 21, 233 (1989)
Benson SW, "Thermochemical Kinetics," 2nd Edition, John Wiley & Sons, New York, N.Y. (1976)
Tran T, Senkan SM, Ind. Eng. Chem. Res., 33(1), 32 (1994)
Ranzi E, Dente M, Rovaglio M, Chem. Eng. Commun., 117, 17 (1992)
Ranzi E, Grottoli MG, Bussani G, Stan CC, Zahng G, LaChim. L'Ind., 75, 261 (1993)
Fessenden RJ, "Organic Chemistry," 5th ed., Brooks/Cole, Pacific Grove, CA (1993)
McMurry J, "Organic Chemistry," 3rd ed., Brooks/Cole, Pacific Grove, CA (1992)
Weissman M, Benson SW, Int. J. Chem. Kinet., 16, 307 (1984)
Weissman M, Benson SW, Prog. Energy Combust. Sci., 15, 273 (1989)
Larson RS, "Plug: A Fortran Program for the ANalysis of Plug Flow Reactors with Gas-Phase and Surface Chemistry," Sandia National Laboratories, Livermore, CA (1987)
Larson RS, "Plug: A Fortran Program for the Analysis of Plug Flow Reactors with Gas-Phase and Surface Chemistry," Sandia National Laboratories, Livermore, CA (1996)
Kee RJ, Rupley FM, Meeks E, Miller JA, "Chemkin-III: A Fortran Chemical Kinetics Package for the Analysis of Gas Phase Chemical and Plasma Kinetics," Sandia National Laboratories, Livermore, CA (1996)
Coltrin ME, "Surface Chemkin III: A Fortran Package for Analyzing Heterogeneous Chemical Kinetics at a Solid Surface-Gas Phase Interfaces," Sandia National Laboratories, Livermore, CA (1996)
Chase MW, Davies CA, Downey JR, Frurip DJ, McDonald RA, Syverud AN, "JANAF Thermochemical Tables Part I," 3rd ed., American Chemical Society, New York, N.Y. (1986)
Steinfeld JI, "Chemical Kinetics and Dynamics," 2nd ed., Prentice-Hall, Upper Saddle River, New Jersey (1998)
Senkan SM, Private Communications (1998)
Karra BS, Senkan SM, Ind. Eng. Chem. Res., 27, 1163 (1988)

[Referenced By]

[Related Articles]

[1] Moon SH, "Petrochemical Engineering," Seoul National University (1997)

[2] Kurtz BE, Ind. Eng. Chem. Proc. Des. Dev., 11, 332 (1972)

[3] Benson SW, Int. J. Chem. Kinet., 21, 233 (1989)

[4] Benson SW, "Thermochemical Kinetics," 2nd Edition, John Wiley & Sons, New York, N.Y. (1976)

[5] Tran T, Senkan SM, Ind. Eng. Chem. Res., 33(1), 32 (1994)

[6] Ranzi E, Dente M, Rovaglio M, Chem. Eng. Commun., 117, 17 (1992)

[7] Ranzi E, Grottoli MG, Bussani G, Stan CC, Zahng G, LaChim. L'Ind., 75, 261 (1993)

[8] Fessenden RJ, "Organic Chemistry," 5th ed., Brooks/Cole, Pacific Grove, CA (1993)

[9] McMurry J, "Organic Chemistry," 3rd ed., Brooks/Cole, Pacific Grove, CA (1992)

[10] Weissman M, Benson SW, Int. J. Chem. Kinet., 16, 307 (1984)

[11] Weissman M, Benson SW, Prog. Energy Combust. Sci., 15, 273 (1989)

[12] Larson RS, "Plug: A Fortran Program for the ANalysis of Plug Flow Reactors with Gas-Phase and Surface Chemistry," Sandia National Laboratories, Livermore, CA (1987)

[13] Larson RS, "Plug: A Fortran Program for the Analysis of Plug Flow Reactors with Gas-Phase and Surface Chemistry," Sandia National Laboratories, Livermore, CA (1996)

[14] Kee RJ, Rupley FM, Meeks E, Miller JA, "Chemkin-III: A Fortran Chemical Kinetics Package for the Analysis of Gas Phase Chemical and Plasma Kinetics," Sandia National Laboratories, Livermore, CA (1996)

[15] Coltrin ME, "Surface Chemkin III: A Fortran Package for Analyzing Heterogeneous Chemical Kinetics at a Solid Surface-Gas Phase Interfaces," Sandia National Laboratories, Livermore, CA (1996)

[16] Chase MW, Davies CA, Downey JR, Frurip DJ, McDonald RA, Syverud AN, "JANAF Thermochemical Tables Part I," 3rd ed., American Chemical Society, New York, N.Y. (1986)

[17] Steinfeld JI, "Chemical Kinetics and Dynamics," 2nd ed., Prentice-Hall, Upper Saddle River, New Jersey (1998)

[18] Senkan SM, Private Communications (1998)

[19] Karra BS, Senkan SM, Ind. Eng. Chem. Res., 27, 1163 (1988)