Risk evaluation on the basis of pressure rate measured by automatic pressure tracking adiabatic calorimeter.

An automatic pressure tracking adiabatic calorimeter (APTAC) had been employed to obtain the thermokinetic and the vapor pressure data during runaway reactions. The APTAC is an adiabatic calorimeter with a large-scale sample mass and low thermal inertia, and is an extremely useful tool for assessing thermal hazards of reactive chemicals. The data obtained by the APTAC are important information for the design of the safe industrial process. The thermodynamics parameters and the gas production were discussed on the basis of the experimental data of various concentrations and weights of di-tert-butyl peroxide (DTBP)/toluene solution for the purpose of investigating the properties of the APTAC data. The thermal decomposition of DTBP was studied on the basis of the temperature data and the pressure data obtained by the APTAC. The activation energy and the frequency factor of DTBP are nearly constant and the same as the literature values in the concentrations between 20 and 60 wt.%. The pressure rise due to gas production is important data for designing the relief vent of a reactor. The time history of the gas production was investigated with various weights and concentrations. The total gas production index, which had the vapor pressure correction, was 1.0 in the decomposition of DTBP.

Risk assessment on processing facility of raw organic garbage.

To investigate the cause of an explosion during disposal processing of raw garbage, the property of the raw garbage was primarily examined by a thermo gravimetry-differential thermal analyzer. With mutable oil concentration, the results showed variable onset temperatures of the exothermal reaction for the samples, for example, decreasing from 150 degrees C in the samples typically containing 10.9-14.1% oil to 114 degrees C when the oil content was raised to 40%. The disposal process was then simulated in a laboratory-scale facility being heated by hot air of 150 degrees C, which was blown into the bottom through nozzles. In the case of the dried garbage containing 14.1% oil, white smoke emitted after several hours, accompanying with an abrupt rise of the temperatures in particular at the bottom of the facility. The maximum temperature reached to 1070 degrees C. Meanwhile, gases, including flammable ones, whose amounts were CO2 approximately CO>H2>methane>ethane in order, were yielded. It indicated that smoldering developed from the zones near the hot air supply nozzle and propagated along the pathway of the imposed air. The continuously released gases possibly induced the transition of smoldering to flame or explosion after accumulating for hours.

Thermal characteristics of lysine tri-isocyanate and its mixture with water.

The thermal reactivity of lysine tri-isocyanate (LTI, 2-isocyanatoethyl-2,6-diisocyanato caproylate) and its mixture with 1% water was investigated after the occurrence of a runaway reaction at a plant. By using a sensitive thermal calorimeter, C80, and an adiabatic calorimeter, ARC, an onset reaction of LTI was observed at 70-100 degrees C and it became vigorous at 175-200 degrees C. The reaction is considered as co-polymerization at this stage, which causes a second decomposition reaction at 200 degrees C if the heat generation is accumulated in the vessel. On the other hand, the presence of water can catalyze LTI at much lower onset temperature and lead to a moderate reaction at 50 degrees C since carbamine is produced and in turn it induces decarbonization of the LTI molecule with significant release of CO2 gas which was detected by a gas chromatography and an FT-IR gas analyzer.

Decomposition of hydroxylamine/water solution with added iron ion.

Decomposition hazards of hydroxylamine (HA)/water solution with and without the addition of iron ion were studied in this paper. Tests were conducted to obtain information about decomposition hazards of HA/water solution following the United Nations recommendations on the transport of dangerous goods. When the heat accumulation storage test was conducted using HA50 wt.%/water solution without the addition of iron ion, the self-accelerating decomposition temperature (SADT) was 80 degrees C. Therefore, HA50 wt.%/water solution was not classified with self-reactive substances following the United Nations recommendations on the transport of dangerous goods. Decomposition hazards of HA50 wt.%/water solution with added iron ion were investigated. The concentration of iron ion in sample of HA50 wt.%/water solution without the addition of iron ion was below 1.0 ppm. The range of the concentration of iron ion in sample of HA50 wt.%/water solution with added iron ion was between 1.0 and 5.4 ppm. The thermal stability of HA50 wt.%/water solution decreased by the addition of iron ion in the heat accumulation storage test. HA50 wt.%/water solution with the addition of iron ion was classified with self-reactive substances following the United Nations recommendations on the transport of dangerous goods. The intensity of the thermal decomposition of HA50 wt.%/water solution increased by the addition of iron ion in the Koenen test.