Evaluation of lower flammability limits of fuel-air-diluent mixtures using calculated adiabatic flame temperatures.

The lower flammability limit (LFL) of a fuel is the minimum composition in air over which a flame can propagate. Calculated adiabatic flame temperatures (CAFT) are a powerful tool to estimate the LFL of gas mixtures. Different CAFT values are used for the estimation of LFL. SuperChems is used by industry to perform flammability calculations under different initial conditions which depends on the selection of a threshold temperature. In this work, the CAFT at the LFL is suggested for mixtures of fuel-air and fuel-air-diluents. These CAFT can be used as the threshold values in SuperChems to calculate the LFL. This paper discusses an approach to evaluate the LFL in the presence of diluents such as N2 and CO2 by an algebraic method and by the application of SuperChems using CAFT as the basis of the calculations. The CAFT for different paraffinic and unsaturated hydrocarbons are presented as well as an average value per family of chemicals.

Evaluation of 1,3-butadiene dimerization and secondary reactions in the presence and absence of oxygen.

Thermal stability evaluation of exothermic chemical reactions is of great importance to the safer design and operation of chemical processes. Dominant reaction stoichiometries and their thermochemistry parameters are key elements in the evaluation process. Identification of significant reaction pathways under possible process conditions will lead to an understanding of the overall thermodynamic and kinetic behavior. The kinetics of 1,3-butadiene (BD) is an excellent example of conjugated dienes that undergo addition reactions. At elevated temperatures, 1,3-butadiene monomers can dimerize exothermally, and as temperature increases, secondary exothermic reactions will take place. The very high temperature and pressure rates that these reactions can attain may lead to a reaction runaway or even a thermal explosion. BD is a vapor at ambient conditions, usually stored as a pressurized liquid, and is a carcinogen, so the experimental evaluation is potentially difficult and hazardous. In this paper, the thermal stability of BD is evaluated. Dimerization and other secondary reactions are investigated by experimental thermal analysis using an automatic pressure adiabatic calorimeter (APTAC), by theoretical computational quantum chemistry methods, and empirical thermodynamic-energy correlations. A theoretical approach is conducted to predict some of the BD reaction behavior. Results are compared to other literature data obtained using different experimental methods.

Use of failure rate databases and process safety performance measurements to improve process safety.

Employing equipment reliability databases can generate a process of continual improvement. This paper suggests a methodology that uses equipment reliability databases, and a process of benchmarking to establish a continual improvement procedure by learning "how others are doing it". A simple decision-making procedure is suggested too, to assist in prioritizing the processes/equipment that are considered to be improved as well as a methodology to measure the improvement.

Evaluation of styrene-acrylonitrile copolymerization thermal stability and runaway behavior.

Evaluation of thermal stability and runaway behavior of any exothermic chemical system is of great importance for the design and operation of a chemical process. The evaluation process should be based on a thorough investigation of the reaction chemistry including reaction pathways, thermodynamic, and kinetic parameters. When addressing the reactivity hazards of any reacting system, the dominant pathway(s) should be identified. Identifying the main reaction pathway under specific conditions will lead to a better thermodynamic and kinetic characterization of the reacting system. In this article, the thermal stability and runaway behavior of styrene-acrylonitrile copolymerization reaction system in bulk is evaluated. Traditional thermal analysis techniques (calorimetric analysis) are combined with computational quantum chemistry methods and empirical thermodynamic-energy correlations. Reaction pathways are identified from the theoretical approach and verified by experimental measurements. The results of this analysis are compared to literature data for this system.

Prediction of reactive hazards based on molecular structure.

There is considerable interest in prediction of reactive hazards based on chemical structure. Calorimetric measurements to determine reactivity can be resource consuming, so computational methods to predict reactivity hazards present an attractive option. This paper reviews some of the commonly employed theoretical hazard evaluation techniques, including the oxygen-balance method, ASTM CHETAH, and calculated adiabatic reaction temperature (CART). It also discusses the development of a study table to correlate and predict calorimetric properties of pure compounds. Quantitative structure-property relationships (QSPR) based on quantum mechanical calculations can be employed to correlate calorimetrically measured onset temperatures, T(o), and energies of reaction, -deltaH, with molecular properties. To test the feasibility of this approach, the QSPR technique is used to correlate differential scanning calorimeter (DSC) data, T(o) and -deltaH, with molecular properties for 19 nitro compounds.

Effect of air in the thermal decomposition of 50 mass% hydroxylamine/water.

This paper presents experimental measurements of 50 mass% hydroxylamine (HA)/water thermal decomposition in air and vacuum environments using an automatic pressure tracking adiabatic calorimeter (APTAC). Overall kinetics, onset temperatures, non-condensable pressures, times to maximum rate, heat and pressure rates versus temperature, and mixture vapor pressures for the experiments in vacuum were similar when compared to the corresponding data for HA decomposition in air. Determined was an overall activation energy of 119+/-8 kJ/mol (29+/-2 kcal/mol), which is low compared to 257 kJ/mol (61.3 kcal/mol) required to break the H(2)N-OH bond reported in the literature. The availability of oxygen from air did not affect detected runaway decomposition products, which were H(2), N(2), N(2)O, NO, and NH(3), for samples run in vacuum or with air above the sample. A delta H(rxn) of -117 kJ/mol (28 kcal/mol) was estimated for the HA decomposition reaction under runaway conditions.

Adiabatic calorimetric decomposition studies of 50 wt.% hydroxylamine/water.

Calorimetric data can provide a basis for determining potential hazards in reactions, storage, and transportation of process chemicals. This work provides calorimetric data for the thermal decomposition behavior in air of 50wt.% hydroxylamine/water (HA), both with and without added stabilizers, which was measured in closed cells with an automatic pressure tracking adiabatic calorimeter (APTAC). Among the data provided are onset temperatures, reaction order, activation energies, pressures of noncondensable products, thermal stability at 100 degrees C, and the effect of HA storage time. Discussed also are the catalytic effects of carbon steel, stainless steel, stainless steel with silica coating, inconel, titanium, and titanium with silica coating on the reaction self-heat rates and onset temperatures. In borosilicate glass cells, HA was relatively stable at temperatures up to 133 degrees C, where the HA decomposition self-heat rate reached 0.05 degrees C/min. The added stabilizers appeared to reduce HA decomposition rates in glass cells and at ambient temperatures. The tested metals and metal surfaces coated with silica acted as catalysts to lower the onset temperatures and increase the self-heat rates.