연속식 SCWO 반응기를 이용하여 DMMP의 초임계수 산화반응을 반응온도 440~540 ℃, 반응압력 242 bar, 체류시간 10~26 초, 과잉산소량 -40~200％의 조건 하에서 수행하였다. 반응온도 540 ℃에서 DMMP 분해율은 99.7％ 이상으로 높았으며, DMMP의 농도가 증가함에 따라 DMMP 분해율은 증가하였다. 산화제 농도 변화에 따른 분해율은 양론비 이하에서는 현저하게 영향을 받았으나, 양론비 이상에서는 큰 차이가 없었다. DMMP 분해율이 85％ 이상인 30개의 실험결과로부터 DMMP의 초임계수 산화반응 속도식을 도출하였다. Pre-exponential factor는 (1.10±0.76)×106, 반응 활성화에너지는 90.66±3.87 kJ/mol, DMMP와 산소에 대한 반응차수는 각각 1.02±0.03, 0.32±0.03로 모델에 의한 예측값과 실험값은 잘 일치하였다.

Supercritical water oxidation of DMMP using continuous flow reactor was studied at temperature ranging from 440 to 540 ℃ and a fixed pressure of 242 bar. The range of residence times in the reactor was from 10 to 26 s, and oxygen excess value varied from -40 to 200％. Destruction efficiencies (DE) of DMMP were greater than 99.7％ at 540 ℃, and increased as the DMMP concentrations were increased. DE of DMMP were significantly affected by oxygen concentration under stoichiometric amount, but showed little difference over stoichiometric amount. On the basis of 30 data with conversions greater than 85％, kinetic correlations for the DE of DMMP were developed. The pre-exponential factor was (1.10±0.76)×106, and the activation energy was 90.66±3.87 kJ/mol, and the reaction orders for DMMP and oxygen were 1.02±0.03, 0.32±0.03, respectively. The model predictions agreed well with the experimental data.

Supercritical Water Oxidation DMMP Kinetics

Watanabe M, Sato T, Inomata H, Smith RL, Arai K, Kruse A, Dinjus E, Chem. Rev., 104(12), 5803 (2004)
Kritzer P, Dinjus E, Chem. Eng. J., 83(3), 207 (2001)
Hodes M, Marrone PA, Hong GT, Smith KA, Tester JW, J. Supercrit. Fluids, 29, 289 (2004)
McBrayer RN, Deaton JE, Eller JM, “Turbulent Flow Cold-wall Reactor,” US Patent 5,552,039 (1996)
Calzavara Y, Joussot-Dubien C, Turc HA, Fauvel E, Sarrade S, J. Supercrit. Fluids, 31, 195 (2004)
Fauvel E, Joussot-Dubien C, Guichardon P, Charbit G, Sarrade S, J. Supercrit. Fluids, 28, 47 (2004)
Casal V, Schmidt H, J. Supercrit. Fluids, 13(1), 269 (1998)
Cocero MJ, Martinez JL, J. Supercrit. Fluids, 31, 41 (2004)
Cohen LS, Jensen D, Lee G, Ordway DW, Waste Manage., 18, 539 (1998)
Haroldsen BL, Ariizumi DY, Mills BE, Brown BG, Rousar DC, “Transpiring wall Supercritical Oxidation Test Reactor Design Report,” Sandia report SAND 96-8213 UC-402 (1996)
McGuinness TG, “Supercritical Oxidation Reactor,” US Patent 5,558,783 (1996)
National Research Council, Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons, National Academy Press. Washington, D.C. (1999)
National Research Council, Analysis of Engineering Design Studies for Demilitarization of Assembled Chemical Weapons at Blue Grass Army Depot, National Academy Press. Washinton, D.C. (2002)
Marrone PA, Cantwell SD, Dalton DW, Ind. Eng. Chem. Res., 44(24), 9030 (2005)
Bianchetta S, Li LX, Gloyna EF, Ind. Eng. Chem. Res., 38(8), 2902 (1999)
Lachance R, Paschkewitz J, DiNaro J, Tester JW, J. Supercrit. Fluids, 16(2), 133 (1999)
Cocero MJ, Martinez JL, J. Supercrit. Fluids, 24, 37 (2002)