Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / by Mohamad Metghalchi. / Sc.D.

The conversion of coal and char nitrogen has been investigated during fuel rich combustion. The experiments were done with the objective of clarifying the roles of NO, HCN, and NH₃, and char nitrogen in the post-combustion gases in the first, fuel rich stage of a staged combustor. The experimental apparatus includes a downflow combustor of 15 cm internal diameter and 180 cm length constructed of fibrous alumina insulation surrounding a central tube composed of vacuum- formed alumina cylinders. The combustion gases and solids were sampled in situ with a water-cooled and -quenched probe. Neither the combustor nor the sample probe were found to be reactive towards NO. Temperatures of the gases and walls were measured with Type K thermocouples and the particle temperatures were determined with a seven wavelength infrared pyrometer. Gas compositions were measured chromatographically using a 5A molecular seive for permanent gases (H₂, O₂, N₂, CO, and CH₄) and Poropak T for polar gases (CO₂ and HCN). A chemiluminescent analyzer measured NO. NH₃ and HCN were measured in the quench water with ion electrodes. The C, H, N, ash compositions of the char were measured with an elemental analyzer. Experiments of the fuel rich conversion of char nitrogen show that at all stoichiometries (SR = 0.8, 0.4) the concentrations of HCN and NH₃ in the post-flame gases are small compared to the concentration of NO. Char nitrogen conversion was stoichiometric or greater. NO destruction was found to be controlled by a heterogeneous mechanism involving the char carbon surface. The mechanism is deactivated by oxygen, an effect demonstrated by others. The fuel rich conversion of coal nitrogen was investigated with a Utah bituminous coal. At moderate fuel rich conditions (SR = 0.8), the residual char nitrogen conversion is 90 percent or greater and NH₃ and HCN concentrations were less than 20 ppmv. NO peaked at 1200 ppmv (1850 K) and declined to 600 (1580 K) ppmv over 1.8 seconds. Coal nitrogen conversion is dominated by NO formation at this stoichiometry. At extreme fuel rich conditions (SR = 0.4), coal nitrogen conversion is 85 percent. The gas is dominated by HCN, NO, and NH₃. HCN decayed from 600 ppm to 300 ppmv, NO from 350 to 50, and NH₃ increased from 200 to 375 ppmv, indicating that interconversion reactions in the gas phase are dominating. The kinetics which govern the volatile nitrogen reactions can be described by global homogeneous kinetics as follows: UNFORMATTED TABLE/EQUATION FOLLOWS: r₁ = d/dt[HCN] = -5.5x10¹⁷ exp(-83.3 K/RT)[HCN][H₂O]/[H₂]¹/² mole/cm³s r₂ = d/dt[NO] = -2.2x10¹⁶ exp(-54.4 K/RT)[NO][NH₃]/[H₂]¹/² d/dt[NH₃] = d/dt[NO] - d/dt[HCN] UNFORMATTED TABLE/EQUATION ENDS These yield rates for free radical reactions very similar to those determined in gas flame experiments, lending credence to their validity. A one-dimensional combustor model has been formulated which accounts for the heterogeneous combustion and gasification of the coal and char. This model includes the devolatilization of the coal and homogeneous oxidation of carbon monoxide and devolatilized species. The water-gas shift reaction is assumed to be equilibrated. The model also includes the mass, momentum and energy balances of the particles but obviates the solution of the combustor heat balance by using the measured gas temperature in the solution. The model accurately predicts the gas and elemental conversions and particle temperatures observed in the experiments, and supports the homogeneous and heterogeneous kinetics of post-combustion fuel nitrogen conversion.

Thesis (doctoral)--Technische Universiteit Delft, 2002. / Vita. Includes bibliographical references.

Thesis (doctoral)--Technische Universiteit Delft, 2002. / Vita. Includes bibliographical references.

A integração da equação da transferência radiante (RTE) é uma tarefa complexa devido a forte variação do coeficiente de absorção com relação ao número de onda. O modelo da soma ponderada dos gases cinza (WSGG) evita a integração linha por linha da RTE reduzindo o esforço computacional na resolução de problemas que envolvam gases participantes. Com a atualização dos coeficientes do WSGG, obtidos através do banco de dados HITEMP 2010, este trabalho se propôs a validá-los por meio de problemas unidimensionais de transferência de calor radiante. Os problemas são resolvidos pelo modelo WSGG e comparados com a solução obtida pela integração LBL (solução benchmark). Nas comparações foram utilizados diferentes perfis de temperatura, distâncias características, gradientes de temperatura e concentrações de espécies. Nos casos analisados é possível verificar uma boa concordância geral entre os resultados WSGG e LBL. O modelo também é testado na resolução de perfis advindos de seções de uma câmara de combustão cilíndrica que apresentaram condições diferentes para os quais os coeficientes WSGG foram propostos. Mesmo assim os resultados obtidos apresentaram uma boa concordância para o termo fonte radiante e para o fluxo de calor, sendo que os maiores erros foram observados na entrada da câmera onde os gradientes de temperatura são mais significativos. / The spectral integration of the radiative transfer equation (RTE) is still a complex task due to the strong variation of the absorption coefficient with the wavenumber. The Weighted-Sumof- Gray-Gases (WSGG) model avoids the Line-by-Line (LBL) integration of RTE. The aim of this study is to evaluate the updated WSGG coefficients, obtained from the database HITEMP 2010, in one-dimensional problems of radiative heat transfer. The problems are solved by the WSGG model and compared with the solution obtained by the LBL integration (benchmark solution). Various temperature and concentration profiles were evaluated and showed a good overall agreement between the WSGG and LBL results. The model was also tested by solving profiles arising from cylindrical combustion chamber and the obtained results showed good agreement for the radiative heat source term and the heat flux. The largest errors were observed near the chamber entrance where the temperature gradients are most significant.

A integração da equação da transferência radiante (RTE) é uma tarefa complexa devido a forte variação do coeficiente de absorção com relação ao número de onda. O modelo da soma ponderada dos gases cinza (WSGG) evita a integração linha por linha da RTE reduzindo o esforço computacional na resolução de problemas que envolvam gases participantes. Com a atualização dos coeficientes do WSGG, obtidos através do banco de dados HITEMP 2010, este trabalho se propôs a validá-los por meio de problemas unidimensionais de transferência de calor radiante. Os problemas são resolvidos pelo modelo WSGG e comparados com a solução obtida pela integração LBL (solução benchmark). Nas comparações foram utilizados diferentes perfis de temperatura, distâncias características, gradientes de temperatura e concentrações de espécies. Nos casos analisados é possível verificar uma boa concordância geral entre os resultados WSGG e LBL. O modelo também é testado na resolução de perfis advindos de seções de uma câmara de combustão cilíndrica que apresentaram condições diferentes para os quais os coeficientes WSGG foram propostos. Mesmo assim os resultados obtidos apresentaram uma boa concordância para o termo fonte radiante e para o fluxo de calor, sendo que os maiores erros foram observados na entrada da câmera onde os gradientes de temperatura são mais significativos. / The spectral integration of the radiative transfer equation (RTE) is still a complex task due to the strong variation of the absorption coefficient with the wavenumber. The Weighted-Sumof- Gray-Gases (WSGG) model avoids the Line-by-Line (LBL) integration of RTE. The aim of this study is to evaluate the updated WSGG coefficients, obtained from the database HITEMP 2010, in one-dimensional problems of radiative heat transfer. The problems are solved by the WSGG model and compared with the solution obtained by the LBL integration (benchmark solution). Various temperature and concentration profiles were evaluated and showed a good overall agreement between the WSGG and LBL results. The model was also tested by solving profiles arising from cylindrical combustion chamber and the obtained results showed good agreement for the radiative heat source term and the heat flux. The largest errors were observed near the chamber entrance where the temperature gradients are most significant.

A integração da equação da transferência radiante (RTE) é uma tarefa complexa devido a forte variação do coeficiente de absorção com relação ao número de onda. O modelo da soma ponderada dos gases cinza (WSGG) evita a integração linha por linha da RTE reduzindo o esforço computacional na resolução de problemas que envolvam gases participantes. Com a atualização dos coeficientes do WSGG, obtidos através do banco de dados HITEMP 2010, este trabalho se propôs a validá-los por meio de problemas unidimensionais de transferência de calor radiante. Os problemas são resolvidos pelo modelo WSGG e comparados com a solução obtida pela integração LBL (solução benchmark). Nas comparações foram utilizados diferentes perfis de temperatura, distâncias características, gradientes de temperatura e concentrações de espécies. Nos casos analisados é possível verificar uma boa concordância geral entre os resultados WSGG e LBL. O modelo também é testado na resolução de perfis advindos de seções de uma câmara de combustão cilíndrica que apresentaram condições diferentes para os quais os coeficientes WSGG foram propostos. Mesmo assim os resultados obtidos apresentaram uma boa concordância para o termo fonte radiante e para o fluxo de calor, sendo que os maiores erros foram observados na entrada da câmera onde os gradientes de temperatura são mais significativos. / The spectral integration of the radiative transfer equation (RTE) is still a complex task due to the strong variation of the absorption coefficient with the wavenumber. The Weighted-Sumof- Gray-Gases (WSGG) model avoids the Line-by-Line (LBL) integration of RTE. The aim of this study is to evaluate the updated WSGG coefficients, obtained from the database HITEMP 2010, in one-dimensional problems of radiative heat transfer. The problems are solved by the WSGG model and compared with the solution obtained by the LBL integration (benchmark solution). Various temperature and concentration profiles were evaluated and showed a good overall agreement between the WSGG and LBL results. The model was also tested by solving profiles arising from cylindrical combustion chamber and the obtained results showed good agreement for the radiative heat source term and the heat flux. The largest errors were observed near the chamber entrance where the temperature gradients are most significant.

A "leveling off" trend in NOx emissions with high amounts of steam addition has been observed in industrial gas turbine diffusion flame combustors. Experiments were performed to try to reproduce this trend in a laminar, opposed flow diffusion flame burner. Experiments were performed with Cli4, C2H4, CO, COIH2 (1:1), and COIH2 (1:2) as fuels. Both hydrocarbon fuels and non-hydrocarbon fuels were tested to study the contribution of the Fenimore mechanism to the "leveling off" trend. Probe sampling with chemiluminescent analysis was used to fmd NOx concentrations; Pt/PtRh thermocouples corrected for radiation losses were used to measure flame temperatures. The experiments reproduced the "leveling off" of NOx emissions, but a "leveling off" of temperatures also occurred. There were no significant differences in the results from the hydrocarbon and non-hydrocarbon fuels. The "leveling off" of NOx emissions is attributed to the "leveling off" of temperatures in the burner. It is not necessary to invoke the Fenimore mechanism to explain this trend. At least 55% of the NOx was eliminated from the flames using steam injection, which implies that at least 55% of the NOx was formed by the Zeldovich mechanism Evidence of Fenimore NO was provided by the fact that the existence of hydrocarbon coking on the fuel nozzle encouraged NOx production in all flames. / Master of Science

Waste-to-energy has become an attractive alternative to landfills. One concern in this development is the release of pollutants in the combustion process. The binder enhanced d-RDF pellets satisfy the requirements of environmental acceptance, chemical/biological stability, and being storeable. The acid gas emissions of combusting d-RDF pellets with sulfur-rich coal were analyzed by ion chromatography and decreased when d-RDF pellets were utilized. The results imply the possibility of using d-RDF pellets to substitute for sulfur-rich coal as fuel, and also substantiate the effectiveness of a binder, calcium hydroxide, in decreasing emissions of SOx. In order to perform the analysis of the combustion sample, sampling and sample pretreatment methods prior to the IC analysis and the first derivative detection mode in IC are investigated as well. At least two trapping reagents are necessary for collecting acid gases: one for hydrogen halides, and the other for NOx and SOx. Factors affecting the absorption of acid gases are studied, and the strength of an oxidizing agent is the main factor affecting the collection of NOx and SOx. The absorption preference series of acid gases are determined and the absorption models of acid gases in trapping reagents are derived from the analytical results. To prevent the back-flushing of trapping reagents between impingers when leak-checking, a design for the sampling train is suggested, which can be adopted in sample collections. Several reducing agents are studied for pretreating the sample collected in alkali-permanganate media. Besides the recommendation of the hydrogen peroxide solution in EPA method, methanol and formic acid are worth considering as alternate reducing agents in the pretreatment of alkaline-permanganate media prior to IC analysis. The first derivative conductivity detection mode is developed and used in IC system. It is efficient for the detection and quantification of overlapping peaks as well as being applicable for non-overlapping peaks.

The impacts of emissions sources of carbon monoxide and particulate matter pollution levels for projected level conformity assessment and National Environmental Policy Act (NEPA) analyses are usually estimated through computer-aided models. Because of the involvement and interaction of a large number of variables that affect formation of CO and PM hot spots, exhaustive impact assessment studies can be time consuming. This is especially true for complex urban projects consisting of numerous roadways whose potential CO and PM impacts on surrounding neighborhoods must be disclosed. A highway project may consist of hundreds of roadway links, therefore undertaking project level conformity analysis without screening tools can be computationally resource intensive. CALINE4, a line source emission modeling tool, is used to predict downwind CO and PM concentrations for various receptors to generate a learning dataset for development of screening rules. This research has developed statistical screening criteria based on Classification and Regression Tree modeling that can be used to eliminate those links from the CALINE4 analysis whose contribution of pollutant concentration to a particular receptor site are insignificant. For the purpose of this study, any link that contributes a concentration of 0 ppm of CO or 0 µg/m3 of PM to a particular receptor site is termed insignificant for the corresponding pollutant. The model uses seven predictor variables, namely wind speed, wind directional variability, linear emission flux, link length and receptor polar coordinates. Response vector has two classes of pollutant concentrations namely significant and insignificant which are obtained by conversion of numerical values of pollutant concentration according to above mentioned criterion, thereby converting a regression problem into categorical or classification problem. The developed rules based on constructed model were validated through test samples and can be applied to future dataset to classify and screen out the insignificant links in highway planning analyses. The screening tool also allows analysts to prepare gridded pollution concentration predictions for use in environmental justice analyses.