Oxidation of Methanol in Supercritical Water

Joo Heon Lee; Neil R. Foster

Journal of Industrial and Engineering Chemistry, Vol.5, No.2, 116-122, June, 1999

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Oxidation of Methanol in Supercritical Water

Joo Heon Lee^†, and Neil R. Foster¹

Department of Environmental Engineering, Taegu University, kyunbuk 712-714, Korea
¹School of Chemical Engineering, University of New South Wales, Sydney 2052, Australia

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Oxidation of methanol in supercritical water has been studied in an isothermal flow reactor over the temperature range 400 ∼500 ℃ at 250 bar. The reaction kinetics were estimated and the oxidation rate was first order with respect to methanol concentration and proportional to oxygen concentration raised to the power of 0.1, The activation energy for methanol oxidation was 193.7 kJ/mol (46.3 kcal/mol) over the temperature range of 400∼475 ℃. The model gave reasonable predictions of the concentrations of methanol, oxygen, carbon monoxide and carbon dioxide. However there were large errors involved with the prediction of hydrogen concentration.

Keywords:supercritical water (SCW);methanol;oxidation;kinetics

[References]

Modell M, U.S. Patent, 4,543,190 (1985)
Modell M, NTIS Paper No. AD-A179005 (1985)
Swallow KC, Killilea WR, Malinowski KC, Staszak CN, Waste Manage., 9, 19 (1989)
Thomason TB, Hong GT, Swallow KC, Killilea WR, Innovative Hazardous Waste Treatment Technology Series: Volume 1: Thermal Processes, H.M. Freeman Ed., p. 31, Technomic Publishing Co., Lancaster PA (1990)
Wightman TJ, M.S. Thesis, University of California, Berkely (1981)
Tester JW, Huff GA, Thomason TB, Swallow KC, Final Report to NASA, Contract NAG2-224, MODAR Inc., Natick (1986)
Helling RK, Tester JW, Energy Fuels, 1, 417 (1987)
Helling RK, Tester JW, Environ. Sci. Technol., 22, 1319 (1988)
Webley PA, Tester JW, SAE Technical Paper Series 881039 (1988)
Webley PA, Tester JW, Energy Fuels, 5, 411 (1991)
Rofer CK, Streit GE, Los Almos National Laboratory Report, LA-11439-MS (DOE/HWP-64), September (1988)
Rofer CK, Streit GE, Los Almos National Laboratory Report, LA-11700-MS (Doe/HWP-90), September (1989)
Dixon CN, Abraham MA, J. Supercrit. Fluids, 5, 269 (1992)
Lee JH, Foster NR, J. Supercrit. Fluids, 9(2), 99 (1996)
Webley PA, Tester JW, ACS Symp. Ser., 406, 226 (1989)
Tester JW, Webley PA, Holgate HR, Ind. Eng. Chem. Res., 32, 236 (1993)
Brock EE, Oshima Y, Savage PE, Barker JR, J. Phys. Chem., 100(39), 15834 (1996)
Lee JH, Ph.D. Thesis, University of New South Wales, Sydney, Australia (1994)
Cutler AH, Antal MJ, Jones M, Ind. Eng. Chem. Res., 27, 691 (1988)
Webley PA, Ph.D. Thesis, Massachusetts Institute of Technology, Cambridge, MA (1989)
Holgate HR, Tester JW, Combust. Sci. Technol., 83, 1 (1992)

[Referenced By]

[Related Articles]

[1] Modell M, U.S. Patent, 4,543,190 (1985)

[2] Modell M, NTIS Paper No. AD-A179005 (1985)

[3] Swallow KC, Killilea WR, Malinowski KC, Staszak CN, Waste Manage., 9, 19 (1989)

[4] Thomason TB, Hong GT, Swallow KC, Killilea WR, Innovative Hazardous Waste Treatment Technology Series: Volume 1: Thermal Processes, H.M. Freeman Ed., p. 31, Technomic Publishing Co., Lancaster PA (1990)

[5] Wightman TJ, M.S. Thesis, University of California, Berkely (1981)

[6] Tester JW, Huff GA, Thomason TB, Swallow KC, Final Report to NASA, Contract NAG2-224, MODAR Inc., Natick (1986)

[7] Helling RK, Tester JW, Energy Fuels, 1, 417 (1987)

[8] Helling RK, Tester JW, Environ. Sci. Technol., 22, 1319 (1988)

[9] Webley PA, Tester JW, SAE Technical Paper Series 881039 (1988)

[10] Webley PA, Tester JW, Energy Fuels, 5, 411 (1991)

[11] Rofer CK, Streit GE, Los Almos National Laboratory Report, LA-11439-MS (DOE/HWP-64), September (1988)

[12] Rofer CK, Streit GE, Los Almos National Laboratory Report, LA-11700-MS (Doe/HWP-90), September (1989)

[13] Dixon CN, Abraham MA, J. Supercrit. Fluids, 5, 269 (1992)

[14] Lee JH, Foster NR, J. Supercrit. Fluids, 9(2), 99 (1996)

[15] Webley PA, Tester JW, ACS Symp. Ser., 406, 226 (1989)

[16] Tester JW, Webley PA, Holgate HR, Ind. Eng. Chem. Res., 32, 236 (1993)

[17] Brock EE, Oshima Y, Savage PE, Barker JR, J. Phys. Chem., 100(39), 15834 (1996)

[18] Lee JH, Ph.D. Thesis, University of New South Wales, Sydney, Australia (1994)

[19] Cutler AH, Antal MJ, Jones M, Ind. Eng. Chem. Res., 27, 691 (1988)

[20] Webley PA, Ph.D. Thesis, Massachusetts Institute of Technology, Cambridge, MA (1989)

[21] Holgate HR, Tester JW, Combust. Sci. Technol., 83, 1 (1992)