Browsing by Subject "Reactive Chemicals"
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Item Evaluation of Alternatives for Safer and More Efficient Reactions: A study of the N-oxidation of Alkylpyridines(2012-02-14) Saenz Noval, Lina RocioThe catalytic N-oxidation of alkylpyridines, a reaction which uses hydrogen peroxide as the oxidizing agent and the water soluble phosphotungstic acid as the catalyst, is a reaction employed in the pharmaceutical industry. The safety concerns of this process revolve around the decomposition of hydrogen peroxide and the liquid-liquid phase separation of the reacting mixture. The decomposition of hydrogen peroxide is an undesired reaction parallel to the desired N-oxidation and is responsible for: 1) a high potential for runaway due to the condition sensitivity of the peroxide group, 2) a potential over-pressurization of the reaction vessel during a runaway due to the production of oxygen, and 3) the enrichment with oxygen of the flammable alkylpyridine environment. The presence of an organic phase and an aqueous phase occurs in a wide range of conditions and results in: 1) a dramatic reduction in the reaction selectivity, and consequently in the efficiency, due to the additional mass transfer constrains imposed by the phase separation, and 2) the safety of the process being seriously compromised because most of the catalyst remains in the aqueous phase, excessively promoting the decomposition of hydrogen peroxide over the N-oxidation. With these concerns in mind, this research aimed to determine conditions for an inherently safer and more efficient N-oxidation reaction and focused on three key targets: i) the possibility of reducing the extend of the decomposition of hydrogen peroxide, thus leading to an inherently safer process, ii) the study of phase equilibrium so as to enable the identification of conditions that increase the efficiency of the N-oxidation and reduces the hazards, and iii) the evaluation of safety parameters that will allow for the control of a potential runaway reaction. Two alkylpyridines were considered: 2-methylpyridine which represents the case of a homogeneous reacting mixture and 2,6-dimethylpyridine to study the two-liquid phase separation effects. The methodology employed calorimetric studies to assess the runaway behavior and to determine the conditions that favor the N-oxidation, and for the N-oxidation of 2,6-dimethylpyridine, thermodynamic studies were incorporated to evaluate the conditions for phase separation.Item The Safe Storage Study for Autocatalytic Reactive Chemicals(2010-10-12) Liu, LijunIn the U.S. Chemical Safety and Hazard Investigation Board (CSB) report, Improving Reactive Hazard Management, there are 37 out of 167 accidents, which occurred in a storage tank or a storage area. This fact demonstrates that thermal runaway problems in chemical storage processes have not been give enough attention. Hydroxylamine Nitrate (HAN) is an important member of the hydroxylamine compound family and its diluted aqueous solution is widely used in the nuclear industry for equipment decontamination. It is also used as a solid or aqueous propellant. Due to its instability and autocatalytic behavior, it has been involved in several incidents at the Hanford and Savannah River Sites (SRS). Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work focuses on extracting its autocatalytic kinetics mechanism and studying its critical behavior from adiabatic calorimetry measurements. The lumped autocatalytic kinetics model, the associated model parameters and HAN critical condition are determined for the first time. The contamination effect of iron ions and nitric acid on diluted hydroxylamine nitrate solution is also studied. This work also identified the safe storage conditions for a small quantity HAN diluted solution with thermal explosion theory. Computational Fluid Dynamics (CFD) was used to further study the influence of natural convection and system scale on the critical behavior for a large quantity of chemical and thus proposed the practical storage guidelines for industrial practice.Item Theoretical and Experimental Evaluation of Chemical Reactivity(2011-10-21) Wang, QingshengReactive chemicals are presented widely in the chemical and petrochemical process industry. Their chemical reactivity hazards have posed a significant challenge to the industries of manufacturing, storage and transportation. The accidents due to reactive chemicals have caused tremendous loss of properties and lives, and damages to the environment. In this research, three classes of reactive chemicals (unsaturated hydrocarbons, self-reacting chemicals, energetic materials) were evaluated through theoretical and experimental methods. Methylcyclopentadiene (MCP) and Hydroxylamine (HA) are selected as representatives of unsaturated hydrocarbons and self-reacting chemicals, respectively. Chemical reactivity of MCP, including isomerization, dimerization, and oxidation, is investigated by computational chemistry methods and empirical thermodynamic?energy correlation. Density functional and ab initio methods are used to search the initial thermal decomposition steps of HA, including unimolecular and bimolecular pathways. In addition, solvent effects are also examined using water cluster methods and Polarizable Continuum Models (PCM) for aqueous solution of HA. The thermal stability of a basic energetic material, Nitroethane, is investigated through both theoretical and experimental methods. Density functional methods are employed to explore the initial decomposition pathways, followed by developing detailed reaction networks. Experiments with a batch reactor and in situ GC are designed to analyze the distribution of reaction products and verify reaction mechanisms. Overall kinetic model is also built from calorimetric experiments using an Automated Pressure Tracking Adiabatic Calorimeter (APTAC). Finally, a general evaluation approach is developed for a wide range of reactive chemicals. An index of thermal risk is proposed as a preliminary risk assessment to screen reactive chemicals. Correlations are also developed between reactivity parameters, such as onset temperature, activation energy, and adiabatic time to maximum rate based on a limited number, 37 sets, of Differential Scanning Calorimeter (DSC) data. The research shows broad applications in developing reaction mechanisms at the molecular level. The methodology of reaction modeling in combination with molecular modeling can also be used to study other reactive chemical systems.