Numerical Simulation of the Thermal Destruction of Some Chlorinated C1 and C2 Hydrocarbons

We have numerically modeled the breakdown of small quantities of several chlorinated hydrocarbons (CH₃CI, CH₂CI₂, CHCI₃, CCI₄, C₂H₃CI, and C₂H₅CI) in a lean mixture of combustion products between 800 and 1480 K. This simulates the fate of poorly atomized waste in a liquid-Injection Incinerator. Kinetics calculations were performed using the CHEMKIN and SENKIN programs, with a reaction mechanism that was developed at Louisiana State University to model flat-flame burner experiments.

A 99.99-percent destruction efficiency was attained In one second at temperatures ranging from 1280 to 960 K, with CCI4 requiring the highest temperature for destruction and C₂H₅CI the lowest. For all compounds except C₂H₅CI, there was a range of temperatures at which byproducts accounted for several percent of the elemental chlorine at the outlet. The more heavily chlorinated compounds formed more byproducts even though the amount of elemental chlorine was the same in all cases. The sensitivity of results to residence time, equivalence ratio, temperature profile, and the presence of additional chlorine, was examined for the case of CHCI₃.     

Evaluation of combustion by-products of MTBE as a component of reformulated gasoline

Methyl tertiary-butyl ether (MTBE) is a gasoline oxygenate that is widely used throughout the US and Europe as an octane-booster and as a means of reducing automotive carbon monoxide (CO) emissions. The combustion by-products of pure MTBE have been evaluated in previous laboratory studies, but little attention has been paid to the combustion by-products of MTBE as a component of gasoline. MTBE is often used in reformulated gasoline (RFG), which has chemical and physical characteristics distinct from conventional gasoline. The formation of MTBE by-products in RFG is not well-understood, especially under "worst-case" vehicle emission scenarios such as fuel-rich operations, cold-starts or malfunctioning emission control systems, conditions which have not been studied extensively. Engine-out automotive dynamometer studies have compared RFG with MTBE to non-oxygenated RFG. Their findings suggest that adding MTBE to reformulated gasoline does not impact the high temperature flame chemistry in cylinder combustion processes. Comparison of tailpipe and exhaust emission studies indicate that reactions in the catalytic converter are quite effective in destroying most hydrocarbon MTBE by-product species. Since important reaction by-products are formed in the post-flame region, understanding changes in this region will contribute to the understanding of fuel-related changes in emissions.     

An experimental and numerical study of the thermal oxidation of chlorobenzene

A combustion-driven flow reactor was used to examine the formation of chlorinated and non-chlorinated species from the thermal oxidation of chlorobenzene under post-flame conditions. Temperature varied from 725 to 1000 K, while the equivalence ratio was held constant at 0.5. Significant quantities of chlorinated intermediates, vinyl chloride and chlorophenol, were measured. A dominant C-Cl scission destruction pathway seen in pyrolytic studies was not observed. Instead, hydrogen-abstraction reactions prevailed, leading to high concentrations of chlorinated byproducts. The thermal oxidation of benzene was also investigated for comparison. Chemical kinetic modeling of benzene and chlorobenzene was used to explore reaction pathways. Two chlorobenzene models were developed to test the hypothesis that chlorobenzene oxidation follows a CO-expulsion breakdown pathway similar to that of benzene. For the temperatures and equivalence ratio studied, hydrogen abstraction by hydroxyl radicals dominates the initial destruction of both benzene and chlorobenzene. Chlorinated byproducts (i.e., chlorophenol and vinyl chloride) were formed from chlorobenzene oxidation in similar quantities and at similar temperatures to their respective analogue formed during benzene oxidation (i.e., phenol and ethylene).     

Excimer laser fragmentation-fluorescence spectroscopy as a method for monitoring ammonium nitrate and ammonium sulfate particles

Excimer laser fragmentation-fluorescence spectroscopy (ELFFS) is shown to be an effective detection strategy for ammonium nitrate and ammonium sulfate particles at atmospheric pressure and room temperature. Following photofragmentation of the ammonium salt particle, fluorescence of the NH fragment is observed at 336 nm. The fluorescence signal is shown to depend linearly on particle surface area for laser intensities varying from 1.2 x 10(8) to 6 x 10(8) W/cm2. The 100 shot (1 s) detection limits for ammonium nitrate range from 20 ppb for 0.2 microm particles to 125 ppb for 0.8 microm particles, where these concentrations are expressed as moles of ammonium ion per mole of air. For ammonium sulfate, the 100 shot (1 s) detection limits vary from 60 ppb for 0.2 microm particles to 500 ppb for 1 microm particles. These detection limits are low enough to measure ammonium salt particles that form in the exhaust of combustion processes utilizing ammonia injection as a nitric oxide control strategy.     

Numerical simulation of the thermal destruction of some chlorinated C1 and C2 hydrocarbons

We have numerically modeled the breakdown of small quantities of several chlorinated hydrocarbons (CH3Cl, CH2Cl2, CHCl3, CCl4, C2H3Cl, and C2H5Cl) in a lean mixture of combustion products between 800 and 1480 K. This simulates the fate of poorly atomized waste in a liquid-injection incinerator. Kinetics calculations were performed using the CHEMKIN and SENKIN programs, with a reaction mechanism that was developed at Louisiana State University to model flat-flame burner experiments. A 99.99-percent destruction efficiency was attained in one second at temperatures ranging from 1280 to 960 K, with CCl4 requiring the highest temperature for destruction and C2H5Cl the lowest. For all compounds except C2H5Cl, there was a range of temperatures at which byproducts accounted for several percent of the elemental chlorine at the outlet. The more heavily chlorinated compounds formed more byproducts even though the amount of elemental chlorine was the same in all cases. The sensitivity of results to residence time, equivalence ratio, temperature profile, and the presence of additional chlorine, was examined for the case of CHCl3.