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The current work, through experimental and numerical investigations, analyses the process and cycle level deviations in engine response on fuelling multi-cylinder natural gas engines with producer gas. Producer gas is a low calorific value bio-derived alternative with composition of 19 ± 1% CO and H2, 2 ± 0.5 % CH4, 12 ± 1% CO2 and 46 ± 1% N2 and has thermo-physical properties significantly different from natural gas. Experimental investigations primarily address the energy balance (full cycle analysis) and in-cylinder response (process specific analysis) at various operating conditions covering naturally aspirated and turbocharged mode of operation with natural gas and producer gas. Numerical investigations are based on two thermodynamic scope mathematical models, a zero dimensional model (Wiebe function) and a quasi-dimensional model (propagating flame front heat release). A detailed diagnostic analysis on a six cylinder (E6) indicates, turbocharger mismatch, the first explicit impact of fuel thermo-physical property variation. Turbocharger matching and optimization resulted in a peak load of 72.8 kWe (BMEP 9.47) at a maximum brake torque ignition angles of 22 deg before TDC and compressor pressure ratio of 2.25. Engine energy distribution analysis indicates skewed energy balance with higher cooling load (in excess of 30%) as compared to fossil fuel operation. This is attributed to the presence of nearly 20% H2 which enhances the convective cooling through the higher thermal conductivity. Parametric variation of H2 fraction on a two cylinder engine (E2) with four different syngas compositions (mixture H2 varying from 7.1% to 14.2%) depicts enhanced cooling load from 33.5% to 37.7%. Process level comparison indicates significant deviations in the heat release profile compared to fossil fuels. It has been observed that with an increase in mixture hydrogen fraction (from 7.1% to 14.2%), the fast burn phase combustion duration reduces from 59.6% to 42.6% but the terminal stage duration increases from 25.5% to 48.9%. The enhanced cooling of the mixture (due to the presence of hydrogen), particularly in the vicinity of walls is argued to contribute towards the sluggish terminal phase combustion. Immediate implication of thermo-kinematic response variation is on the magnitude and sensitivity of combustion descriptors and the need for dependent control system calibration for producer gas fuelled operation is established. Descriptor analysis is extended to knocking pressure traces and a new simple methodology is proposed towards identifying the occurrence and regime of knock. Analysing the implications through numerical investigation, the influence of the altered thermo-kinematic response for producer gas fuelled operation impacts 0D simulations. Zero dimensional simulations fail with conventional coefficients requiring fuel specific coefficients. Based on fuel specific coefficients, the suitability of 0D model for the simulation of varying operating conditions ranging from naturally aspirated to turbo charged engines, compression ratios and different engine geometries is established. The analysis is extended to quasi-dimensional through the eddy entrainment and laminar burn up model. The choice of laminar flame speed and turbulent parameters is validated based on the assessment of the flame speed ratio (4.5 ± 0.5 for naturally aspirated operation, turbulent Reynolds number of 2500 ± 250 and 9.0 ± 1.0 for turbocharged operation, turbulent Reynolds number of 5250 ± 250). In the estimation of laminar flame speed, the limitation of GRIMech 3.0 mechanism for H2-CO-CH4 systems is explicitly established and GRIMech 2.11 is used to arrive at experimentally comparable results. In-cylinder engine simulation results covering parametric variation of load, ignition angle and mixture quality, for engine natural gas fuelled naturally aspirated operation and producer gas fuelled naturally aspirated and turbocharged after cooled are compared with experimental results. The quasi dimensional analysis is extended to simulate end gas auto-ignition and is validated by using experimental manifold conditions for turbocharged operation for which knock has been observed. Extending the model to a Waukesha cooperative fuels research engine, motor methane number of 110 is reported for standard composition producer gas. The use of quasi dimensional models with end gas reaction kinetics enabled for knock rating of fuels represents first of its kind initiative.

Part B of two Project Reports; Part A can be found at: http://hdl.handle.net/11375/16881 / <p> Procedures have been set up to calculate the reactor kinetics parameters for thorium fuelled CANDU reactors using the perturbation option of the 2-dimensional diffusion code EXTERMINATOR. The procedures are believed to be very accurate. </p> <p> Representative cases of a CANDU thorium converter at different stages during the reactor life have been used to test the developed procedures. Results are presented and discussed. </p> / Thesis / Master of Engineering (ME)

In-cylinder fuel-air mixing in a compressed natural gas (CNG)-fuelled, single-cylinder, spark-ignited engine is analysed using a transient three-dimensional computational fluid dynamic model built and run using STAR-CD, a commercial CFD software. This work is motivated by the need for strategies to achieve improved performance in engines utilizing gaseous fuels such as CNG. The transient in-cylinder fuel-air mixing is evaluated for a port gas injection fuelling system and compared with that of conventional gas carburetor system. In this work pure methane is used as gaseous fuel for all the computational studies. It is observed that compared to the premixed gas carburetor system, a substantial level of in-cylinder stratification can be achieved with the port gas injection system. The difference of more than 20% in mass fraction between the rich and lean zones in the combustion chamber is observed for the port gas injection system compared to less than 1% for the conventional premixed system. The phenomenon of stratification observed is very close to the “barrel stratification” mode. A detailed parametric study is undertaken to understand the effect of various injection parameters such as injection location, injection orientation, start of injection, duration of injection and rate of injection. Furthermore, the optimum injection timing is evaluated for various load-speed conditions of the engine. It is also observed that the level of stratification is highest at 50% engine load with a reduced level at 100% load. For low engine loads, the level of stratification is observed to be very low. To analyse the effect of stratification on engine performance, the in-cylinder combustion is modeled using the extended coherent flame model(ECFM). For simulating the ignition process, the arc and kernel tracking ignition model(AKTIM) is used. The combustion model is first validated with measured in-cylinder pressure data and other derived quantities such as heat release rate and mass burn fraction. It is observed that there is a good agreement between measured and simulated values. Subsequently, this model is use to simulate both premixed and stratified cases. It is observed that there is a marginal improvement in terms of overall engine efficiency when the stoichiometric premixed case is compared with the lean stratified condition. However, a major improvement in performance is observed when the lean stratified case is compared with lean premixed condition. The stratified case shows a faster heat release rate which could potentially translate to lower cycle-to-cycle variations in actual engine operation. Also, the stratified cases show as much as 20% lower in-cylinder NOx emissions when compared with the conventional premixed case at the same engine load and speed, underscoring the potential of in-cylinder stratification to achieve improved performance and lower NOx emissions.

In recent decades, the use of fossil fuels has increased exponentially with a corresponding sharp increase in the pollution of the environment. The need for clean and sustainable technologies for the generation of power with reduced or zero environment impact has become critical. A number of attempts have been made to address this problem; one of the most promising attempts is polygeneration. Polygeneration technology is highly efficient and produces lower emissions than conventional methods of power generation because of the simultaneous generation of useable heat and electrical power from a single source of fuel. The overall efficiency of such systems can be as high as 90%, compared to 30-35% for conventional single-product power plants. A number of different technologies are available for polygeneration, such as micro gas turbines, sterling engines, solar systems, and fuel cells. Of these, fuel cell systems offer the most promising technology for polygeneration because of their ability to produce electricity and heat at a high efficiency (about 80%) with either low or zero emissions. Various fuel-cell technologies can be used in polygeneration systems. Of these, solid oxide fuel cells (SOFCs) are the most suitable because they offer high system efficiency for the production of electricity and heat (about 90%) coupled with low or zero emissions. Compared to other types of fuel cells, SOFCs have fuel flexibility (direct operation on hydrocarbon fuels, such as biogas, bio-ethanol, bio-methanol, etc.) and produce high-quality heat energy. The development of polygeneration systems using SOFCs has generally followed one of two approaches. The first approach involves the design of a SOFC system that operates at a temperature of 850 oC and uses natural gas as a fuel. The second approach uses low-temperature (generally 400-600 oC) SOFC (LTSOFC) systems with biomass, e.g., syngas or liquid fuels, such as bio-methanol and bio-ethanol. The latter systems have strong potential for use in polygeneration. High-temperature SOFCs have obvious disadvantages, and challenges remain for lowering the cost to meet commercial interest. The SOFC systems need lower operating temperatures to reduce their overall costs. This thesis focuses on the development of nanocomposites for advanced fuel-cell technology (NANOCOFC), i.e., the next generation SOFCs, which are low-temperature (400-600 oC), marketable, and affordable SOFCs. In addition, new concepts that pertain to fuel-cell science and technology—NANOCOFC (www.nanocofc.com)—are explored and developed. The content of this thesis is divided into five parts: In the first part of this thesis (Papers 1-5), the two-phase nanocomposite electrolytes, viz. ceria-salt and ceria-oxide, were prepared and studied using different electrochemical techniques. The microstructure and morphology of the composite electrolytes were characterised using XRD, SEM and TEM, and the thermal analysis was conducted using DSC. An ionic conductivity of 0.1 S/cm was obtained at 300 ºC, which is comparable to that of conventional YSZ operating at 1000 ºC. The maximum output power density was 1000 mW/cm2 at 550 oC. A co-doped ceria-carbonate was also developed to improve the ionic conductivity, morphology, and performance of the electrolyte. In the second part of this thesis (Papers 7-9), composite electrodes that contained less or no nickel (Ni) were developed for a low-temperature SOFC. All of the elements were highly homogenously distributed in the composite electrode, which resulted in high catalytic activity and good ASOFC performance. The substitution of Ni by Zn in these electrodes could reduce their cost by a factor of approximately 25. In the third part of this thesis (Papers 10), an advanced multi-fuelled solid-oxide fuel cell (ASOFC) with functional nanocomposites (electrolytes and electrodes) was developed. Several different types of fuel, such as gaseous (hydrogen and biogas) and liquid fuels (bio-ethanol and bio-methanol), were tested. Maximum power densities of 1000, 300, 600, and 550 mW/cm2 were achieved with hydrogen, bio-gas, bio-methanol, and bio-ethanol, respectively, in the ASOFC. Electrical and total efficiencies of 54% and 80%, respectively, were achieved when the single cell was used with hydrogen. The fourth part of this thesis (Papers 11) concerns the design of a 5 kW ASOFC system based on the demonstrated advanced SOFC technology. A polygeneration system based on a low-temperature planar SOFC was then designed and simulated. The efficiency of the overall system was approximately 80%. The fifth part of this thesis (Paper 12) describes a single-layer multi-fuelled electrolyte-free fuel cell that is a revolutionary innovation in renewable-energy sources. Conventional fuel cells generate electricity by ion transport through the electrolyte. However, this new device works without an electrolyte, and all of the processes occur at particle surfaces in the material. Based on a theoretical calculation, an additional 18% enhancement of the fuel cell’s efficiency will be achieved using this new technology compared to the conventional technologies. Our developed ASOFC systems with functional nanocomposites offer significant advantages in reducing the operational and capital costs for the production of power and heat by using different fuels based on the fuel-cell technology. ASOFC systems can be used for polygeneration with renewable fuels (i.e., biomass fuels) at high efficiency as a sustainable solution to energy generation in our society. The results have been achieved for this thesis work has demonstrated an advanced fuel cell technology. / <p>QC 20111213</p>

Las celdas de combustible de óxido sólido (cuyo acrónimo en inglés es SOFC) son dispositivos energéticos capaces de convertir la energía química de un combustible directamente en energía eléctrica. Esto las dota de unas eficiencias eléctricas muy elevadas, que pueden llegar a ser del 80% si se aprovecha su calor residual de alta calidad mediante turbinas. Además, son capaces de funcionar con una gran variedad de combustibles: hidrógeno, gas natural, gas de síntesis, etanol, metanol, etc. Sin embargo, para su inserción en la cadena de producción energética, su temperatura de funcionamiento debería disminuir al rango de 500-700 ºC sin que se redujeran las densidades de potencias eléctricas generadas. Las SOFC convencionales se basan en la conducción de iones oxígeno de su electrolito, que separa la reacción de combustión del combustible en sus semi-reacciones electroquímicas, generando de este modo la energía eléctrica directamente. Al disminuir la temperatura de operación en este tipo de SOFC, con electrolitos (o membranas) delgados e hidrógeno como combustible, la principal limitación de funcionamiento se centra en la activación y reducción del oxígeno que tiene lugar en el electrodo denominado cátodo. Por otro lado, el empleo de otros combustibles basados en carbono no es compatible con los materiales de ánodos actualmente utilizados. Por tanto, es necesario el desarrollo de nuevos cátodos con mejoradas propiedades electrocatalíticas para la reducción de oxígeno a menores temperaturas, cuyas propiedades termo-mecánicas sean compatibles con las del resto de componentes de la celda, y la obtención de ánodos capaces de funcionar con combustibles basados en carbono. La combinación conjunta de varios lantánidos y bario en la estructura perovskita (LalPrpSmsBab)0.58Sr0.4Fe0.8Co0.2O3 ha permitido obtener compuestos con resistencias de polarización de electrodo significantemente menores que las mostradas por el cátodo del estado de la técnica La0.6Sr0.4Fe0.8Co0.2O3 en el rango de temperaturas 450-650 ºC. / Vert Belenguer, VB. (2011). ELECTRODOS AVANZADOS PARA PILAS DE COMBUSTIBLE DE ÓXIDO SÓLIDO (SOFCs) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/14669 / Palancia

Doctor of Philosophy(PhD) / Abstract This thesis employs a statistical regression method to estimate models for testing the hypothesis of the thesis of vehicle emissions interdependencies. The thesis at the beginnings, reviews critically the formation of emissions in gasoline-fuelled engines, and also reviews existing and emerging models of automotive emissions. The thesis then, presents the relationships between the urban transport system and vehicle emissions. Particularly, it summarises different types of emissions and the contributory factors of the urban transport system to such emissions. Subsequently, the thesis presents the theory of vehicle emissions interdependencies and the empirical framework for testing the hypothesis of the thesis. The scope of testing the hypothesis of the thesis is only limited to gasoline-fuelled conventional vehicles in the urban transport environment. We use already available laboratory-based testing dataset of 542 passenger vehicles, to investigate the hypothesis of the thesis of vehicle emissions interdependencies. HC, CO, and NOX emissions were collected under six test drive-cycles, for each vehicle before and after vehicles were tuned. Prior to using any application, we transform the raw dataset into actionable information. We use three steps, namely conversion, cleaning, and screening, to process the data. We use classification and regression trees (CART) to narrow down the input number of variables in the models formulated for investigating the hypothesis of the thesis. We then, utilise initial results of the analysis to fix any remaining problems in the data. We employ three stage least squares (3SLS) regression to test the hypothesis of the thesis, and to estimate the maximum likelihood of vehicle variables and other emissions to influence HC, CO, and NOX emissions simultaneously. We estimate twelve models, each of which consists of a system of three simulations equations that accounts for the endogenous relations between HC, CO and NOX emissions when estimating vehicle emissions simultaneously under each test drive-cycle. The major contribution of the thesis is to investigate the inter-correlations between vehicle emissions within a well controlled data set, and to test the hypothesis of vehicle emissions interdependencies. We find that HC, CO, and NOX are endogenously or jointly dependent in a system of simultaneous-equations. The results of the analysis demonstrate that there is strong evidence against the null hypothesis (H0) in favour of the alternative hypothesis (H1) that HC, CO, and NOX are statistically significantly interdependent. We find, for the thesis sample, that NOX and CO are negatively related, whereas HC and CO emissions are positively related, and HC and NOX are positively related. The results of the thesis yield new insights. They bridge a very important gap in the current knowledge on vehicle emissions. They advance not only our current knowledge that HC, CO, and NOX should be predicted jointly since they are produced jointly, but also acknowledge the appropriateness of using 3SLS regression for estimating vehicle emissions simultaneously. The thesis measures the responses of emissions to changes with respect to changes in the other emissions. We investigate emission responses to a one percent increase in an emission with respect to the other emissions. We find the relationship between CO and NOX is of special interest. After vehicles were tuned, we find those vehicles that exhibit a one percent increase in NOX exhibit simultaneously a 0.35 percent average decrease in CO. Similarly, we find that vehicles which exhibit a one percent increase in CO exhibit simultaneously a 0.22 percent average decrease in NOX. We find that the responses of emission to changes with respect to other emissions vary with various test drive-cycles. Nonetheless, a band of upper and lower limits contains these variations. After vehicle tuning, a one percent increase in HC is associated with an increase in NOX between 0.5 percent and 0.8 percent, and an increase in CO between 0.5 percent and one percent Also, for post-tuning vehicles, a one percent increase in CO is associated with an increase in HC between 0.4 percent and 0.9 percent, and a decrease in NOX between 0.07 percent and 0.32 percent. Moreover, a one percent increase in NOX is associated with increase in HC between 0.8 percent and 1.3 percent, and a decrease in CO between 0.02 percent and 0.7 percent. These measures of the responses are very important derivatives of the hypothesis investigated in the thesis. They estimate the impacts of traffic management schemes and vehicle operations that target reducing one emission, on the other non-targeted emissions. However, we must be cautious in extending the results of the thesis to the modern vehicles fleet. The modern fleet differs significantly in technology from the dataset that we use in this thesis. The dataset consists of measurements of HC, CO, and NOX emissions for 542 gasoline-fuelled passenger vehicles, under six test drive-cycles, before and after the vehicles were tuned. Nevertheless, the dataset has a number of limitations such as limited model year range, limited representations of modal operations, and limitations of the measurements of emissions based only on averages of test drive-cycles, in addition to the exclusion of high-emitter emission measurements from the dataset. The dataset has a limited model year range, i.e., between 1980 and 1991. We highlight the age of the dataset, and acknowledge that the present vehicle fleet varies technologically from the vehicles in the dataset used in this thesis. Furthermore, the dataset has a limited number of makes - Holden, Ford, Toyota, Nissan, and Mitsubishi. There are also a limited number of modal operations. The model operations presented in the dataset are cold start, warming-up, and hot stabilised driving conditions. However, enrichment episodes are not adequately presented in the test-drive cycles of the dataset. Moreover, the dataset does not take into account driving behaviour influences, and all measurements are cycle-based averages. The emission measurements of laboratory-based testings are aggregated over a test drive cycle, and the test drive-cycle represents an average trip over an average speed. The exclusion of the measurements of high emitting vehicles from the dataset introduces further limitations. Remote sensing studies show that 20 percent of the on-road vehicle fleet is responsible for 80 percent of HC and CO emissions. The findings of the thesis assist in the identification of the best strategies to mitigate the most adverse effects of air-pollution, such as the most severe pollution that have the most undesirable pollution effects. Also, they provide decision-makers with valuable information on how changes in the operation of the transport system influence the urban air-quality. Moreover, the thesis provides information on how vehicle emissions affect the chemistry of the atmosphere and degrade the urban air-quality.

Doctor of Philosophy(PhD) / Abstract This thesis employs a statistical regression method to estimate models for testing the hypothesis of the thesis of vehicle emissions interdependencies. The thesis at the beginnings, reviews critically the formation of emissions in gasoline-fuelled engines, and also reviews existing and emerging models of automotive emissions. The thesis then, presents the relationships between the urban transport system and vehicle emissions. Particularly, it summarises different types of emissions and the contributory factors of the urban transport system to such emissions. Subsequently, the thesis presents the theory of vehicle emissions interdependencies and the empirical framework for testing the hypothesis of the thesis. The scope of testing the hypothesis of the thesis is only limited to gasoline-fuelled conventional vehicles in the urban transport environment. We use already available laboratory-based testing dataset of 542 passenger vehicles, to investigate the hypothesis of the thesis of vehicle emissions interdependencies. HC, CO, and NOX emissions were collected under six test drive-cycles, for each vehicle before and after vehicles were tuned. Prior to using any application, we transform the raw dataset into actionable information. We use three steps, namely conversion, cleaning, and screening, to process the data. We use classification and regression trees (CART) to narrow down the input number of variables in the models formulated for investigating the hypothesis of the thesis. We then, utilise initial results of the analysis to fix any remaining problems in the data. We employ three stage least squares (3SLS) regression to test the hypothesis of the thesis, and to estimate the maximum likelihood of vehicle variables and other emissions to influence HC, CO, and NOX emissions simultaneously. We estimate twelve models, each of which consists of a system of three simulations equations that accounts for the endogenous relations between HC, CO and NOX emissions when estimating vehicle emissions simultaneously under each test drive-cycle. The major contribution of the thesis is to investigate the inter-correlations between vehicle emissions within a well controlled data set, and to test the hypothesis of vehicle emissions interdependencies. We find that HC, CO, and NOX are endogenously or jointly dependent in a system of simultaneous-equations. The results of the analysis demonstrate that there is strong evidence against the null hypothesis (H0) in favour of the alternative hypothesis (H1) that HC, CO, and NOX are statistically significantly interdependent. We find, for the thesis sample, that NOX and CO are negatively related, whereas HC and CO emissions are positively related, and HC and NOX are positively related. The results of the thesis yield new insights. They bridge a very important gap in the current knowledge on vehicle emissions. They advance not only our current knowledge that HC, CO, and NOX should be predicted jointly since they are produced jointly, but also acknowledge the appropriateness of using 3SLS regression for estimating vehicle emissions simultaneously. The thesis measures the responses of emissions to changes with respect to changes in the other emissions. We investigate emission responses to a one percent increase in an emission with respect to the other emissions. We find the relationship between CO and NOX is of special interest. After vehicles were tuned, we find those vehicles that exhibit a one percent increase in NOX exhibit simultaneously a 0.35 percent average decrease in CO. Similarly, we find that vehicles which exhibit a one percent increase in CO exhibit simultaneously a 0.22 percent average decrease in NOX. We find that the responses of emission to changes with respect to other emissions vary with various test drive-cycles. Nonetheless, a band of upper and lower limits contains these variations. After vehicle tuning, a one percent increase in HC is associated with an increase in NOX between 0.5 percent and 0.8 percent, and an increase in CO between 0.5 percent and one percent Also, for post-tuning vehicles, a one percent increase in CO is associated with an increase in HC between 0.4 percent and 0.9 percent, and a decrease in NOX between 0.07 percent and 0.32 percent. Moreover, a one percent increase in NOX is associated with increase in HC between 0.8 percent and 1.3 percent, and a decrease in CO between 0.02 percent and 0.7 percent. These measures of the responses are very important derivatives of the hypothesis investigated in the thesis. They estimate the impacts of traffic management schemes and vehicle operations that target reducing one emission, on the other non-targeted emissions. However, we must be cautious in extending the results of the thesis to the modern vehicles fleet. The modern fleet differs significantly in technology from the dataset that we use in this thesis. The dataset consists of measurements of HC, CO, and NOX emissions for 542 gasoline-fuelled passenger vehicles, under six test drive-cycles, before and after the vehicles were tuned. Nevertheless, the dataset has a number of limitations such as limited model year range, limited representations of modal operations, and limitations of the measurements of emissions based only on averages of test drive-cycles, in addition to the exclusion of high-emitter emission measurements from the dataset. The dataset has a limited model year range, i.e., between 1980 and 1991. We highlight the age of the dataset, and acknowledge that the present vehicle fleet varies technologically from the vehicles in the dataset used in this thesis. Furthermore, the dataset has a limited number of makes - Holden, Ford, Toyota, Nissan, and Mitsubishi. There are also a limited number of modal operations. The model operations presented in the dataset are cold start, warming-up, and hot stabilised driving conditions. However, enrichment episodes are not adequately presented in the test-drive cycles of the dataset. Moreover, the dataset does not take into account driving behaviour influences, and all measurements are cycle-based averages. The emission measurements of laboratory-based testings are aggregated over a test drive cycle, and the test drive-cycle represents an average trip over an average speed. The exclusion of the measurements of high emitting vehicles from the dataset introduces further limitations. Remote sensing studies show that 20 percent of the on-road vehicle fleet is responsible for 80 percent of HC and CO emissions. The findings of the thesis assist in the identification of the best strategies to mitigate the most adverse effects of air-pollution, such as the most severe pollution that have the most undesirable pollution effects. Also, they provide decision-makers with valuable information on how changes in the operation of the transport system influence the urban air-quality. Moreover, the thesis provides information on how vehicle emissions affect the chemistry of the atmosphere and degrade the urban air-quality.