Flammability hazards of lower aliphatic aldehydes at elevated pressure and temperature



A large and potentially hazardous decrease in aldehyde autoignition temperature (AIT) occurs with increased pressure. The AIT-pressure curve determined in a 5 L stainless steel sphere was similar for propionaldehyde and butyraldehyde in air, falling from about 185°C at atmospheric pressure to 90°C at 140 psia. Reduction of oxygen concentration had little effect on propionaldehyde AIT. At 100°C and 140 psia, autoignitions accompanied by at least a doubling of pressure were observed above 4% oxygen. In the presence of a few grams of free liquid, propionaldehyde vapor ignited in air at initial conditions significantly below the AIT. The mechanism appears to involve rapid Fe-catalyzed exothermic liquid-phase oxidation leading to autoignition of the adjacent heated gas layer. An acetaldehyde vapor-air mixture in the presence of free liquid and rust exploded at room temperature when air pressure was increased to 95 psia; this result is discussed with reference to a cylinder overpressurization that occurred while making up an ostensibly sub-LFL calibration mixture with compressed air. Propionaldehyde's limiting oxygen concentration (LOC) was investigated in the near-autoignition region using the same 5L apparatus; the findings are discussed with reference to an overpressurization incident in an air-liquid partial oxidation reactor. The general results are used to illustrate the application of LOC in partial oxidation processes subject to autoignition and to discuss elements of the current ASTM draft test method for LOC, which does not address test difficulties associated with condensable and/or reactive gas systems.