Thesis (Ph. D.)--Worcester Polytechnic Institute. / Keywords: Water; Adsorption; Molecular simulation; Nanoporous materials. Includes bibliographical references (p. 117-119).

A velocidade de propagação da chama em motores ciclo Otto é determinante das características do combustível, sendo fundamental seu conhecimento para um melhor ajuste do par motor/combustível. Maior velocidade de propagação da chama possibilita aumentar a potência com o aumento da rotação do motor. Assim, pode-se inclusive atrasar o avanço de ignição, com isto, menor será o trabalho negativo necessário para comprimir a mistura já em combustão antes do Ponto Morto Superior, e, maior será a eficiência do ciclo. A velocidade de propagação da chama é fortemente influenciada pela relação de compressão, condição de mistura, turbulência e avanço de ignição. Este trabalho tem como objetivo analisar a influência destes parâmetros de operação na velocidade de propagação da chama em um motor CFR (Cooperative Fuel Research). Para tanto são apresentados resultados experimentais de medidas de ângulo entre o momento de ignição do combustível e a detecção da chama na extremidade oposta da câmara de combustão por um sensor de ionização em um motor CFR. Também é mapeado o trabalho no diagrama pressão versus volume, que permite a avaliação do trabalho líquido produzido por ciclo e disponibiliza o valor do pico de pressão, o ângulo em que este ocorre, a pressão média efetiva e a curva de fração mássica queimada para cada condição ensaiada. Apresenta-se as análises da variação do ângulo de combustão tanto do MTBE quanto do isooctano em 5 diferentes avanços de ignição. Para o ensaio com etanol hidratado são apresentadas as análises realizadas com 6 relações de compressão, 5 avanços de ignição e 5 relações ar-combustível, onde todos os valores destes parâmetros em estudo abrangem faixas típicas de operação de motores comerciais. Os resultados indicam um menor ângulo de combustão para relações de compressão elevadas, condição de mistura ligeiramente rica e elevados avanços de ignição. / The flame speed propagation in Otto cycles engine is a conclusive fuel feature, whose knowledge has a fundamental importance for a better accuracy of the pair engine/fuel. The higher flame speed propagation enables a greater cylinder filling, which can also increase power with improvements in engine speed, as a result holding back the ignition advance. Thus, it will be necessary a lower negative work to compress the mixture already in combustion before the top dead center, then resulting a greater efficiency cycle. The flame speed propagation is highly influenced by the compression ratio, mixture condition and ignition advance. This thesis proposes to investigate the influence of these operational parameters over the flame speed propagation in a CFR engine [Cooperative Fuel Research]. In this way, the angle measurements are performed between the fuel ignition timing and the flame detection over the opposite edge of combustion chamber by a ionization sensor in a CFR engine, as well as the diagram work pressure versus volume, which allows the net work evaluation produced by cycles and available the high pressure value, the angle with this occurs, the mean effective pressure and the curve of mass fraction burned for each tease condition. It introduces the analysis of combustion duration variation as much MTBE as the isooctane in 5 distinct ignition advance for the hydratated ethanol testing are introduced analysis accomplished with 6 compression ratio, 5 ignition advances and 5 air/fuel ratio, whose parameters values studies incorporates typical operational ratios of commercial engines. The results indicated a low angular combustion duration for the higher compression ratio, slightly rich mixture condition and elevated ignition advance.

A velocidade de propagação da chama em motores ciclo Otto é determinante das características do combustível, sendo fundamental seu conhecimento para um melhor ajuste do par motor/combustível. Maior velocidade de propagação da chama possibilita aumentar a potência com o aumento da rotação do motor. Assim, pode-se inclusive atrasar o avanço de ignição, com isto, menor será o trabalho negativo necessário para comprimir a mistura já em combustão antes do Ponto Morto Superior, e, maior será a eficiência do ciclo. A velocidade de propagação da chama é fortemente influenciada pela relação de compressão, condição de mistura, turbulência e avanço de ignição. Este trabalho tem como objetivo analisar a influência destes parâmetros de operação na velocidade de propagação da chama em um motor CFR (Cooperative Fuel Research). Para tanto são apresentados resultados experimentais de medidas de ângulo entre o momento de ignição do combustível e a detecção da chama na extremidade oposta da câmara de combustão por um sensor de ionização em um motor CFR. Também é mapeado o trabalho no diagrama pressão versus volume, que permite a avaliação do trabalho líquido produzido por ciclo e disponibiliza o valor do pico de pressão, o ângulo em que este ocorre, a pressão média efetiva e a curva de fração mássica queimada para cada condição ensaiada. Apresenta-se as análises da variação do ângulo de combustão tanto do MTBE quanto do isooctano em 5 diferentes avanços de ignição. Para o ensaio com etanol hidratado são apresentadas as análises realizadas com 6 relações de compressão, 5 avanços de ignição e 5 relações ar-combustível, onde todos os valores destes parâmetros em estudo abrangem faixas típicas de operação de motores comerciais. Os resultados indicam um menor ângulo de combustão para relações de compressão elevadas, condição de mistura ligeiramente rica e elevados avanços de ignição. / The flame speed propagation in Otto cycles engine is a conclusive fuel feature, whose knowledge has a fundamental importance for a better accuracy of the pair engine/fuel. The higher flame speed propagation enables a greater cylinder filling, which can also increase power with improvements in engine speed, as a result holding back the ignition advance. Thus, it will be necessary a lower negative work to compress the mixture already in combustion before the top dead center, then resulting a greater efficiency cycle. The flame speed propagation is highly influenced by the compression ratio, mixture condition and ignition advance. This thesis proposes to investigate the influence of these operational parameters over the flame speed propagation in a CFR engine [Cooperative Fuel Research]. In this way, the angle measurements are performed between the fuel ignition timing and the flame detection over the opposite edge of combustion chamber by a ionization sensor in a CFR engine, as well as the diagram work pressure versus volume, which allows the net work evaluation produced by cycles and available the high pressure value, the angle with this occurs, the mean effective pressure and the curve of mass fraction burned for each tease condition. It introduces the analysis of combustion duration variation as much MTBE as the isooctane in 5 distinct ignition advance for the hydratated ethanol testing are introduced analysis accomplished with 6 compression ratio, 5 ignition advances and 5 air/fuel ratio, whose parameters values studies incorporates typical operational ratios of commercial engines. The results indicated a low angular combustion duration for the higher compression ratio, slightly rich mixture condition and elevated ignition advance.

A velocidade de propagação da chama em motores ciclo Otto é determinante das características do combustível, sendo fundamental seu conhecimento para um melhor ajuste do par motor/combustível. Maior velocidade de propagação da chama possibilita aumentar a potência com o aumento da rotação do motor. Assim, pode-se inclusive atrasar o avanço de ignição, com isto, menor será o trabalho negativo necessário para comprimir a mistura já em combustão antes do Ponto Morto Superior, e, maior será a eficiência do ciclo. A velocidade de propagação da chama é fortemente influenciada pela relação de compressão, condição de mistura, turbulência e avanço de ignição. Este trabalho tem como objetivo analisar a influência destes parâmetros de operação na velocidade de propagação da chama em um motor CFR (Cooperative Fuel Research). Para tanto são apresentados resultados experimentais de medidas de ângulo entre o momento de ignição do combustível e a detecção da chama na extremidade oposta da câmara de combustão por um sensor de ionização em um motor CFR. Também é mapeado o trabalho no diagrama pressão versus volume, que permite a avaliação do trabalho líquido produzido por ciclo e disponibiliza o valor do pico de pressão, o ângulo em que este ocorre, a pressão média efetiva e a curva de fração mássica queimada para cada condição ensaiada. Apresenta-se as análises da variação do ângulo de combustão tanto do MTBE quanto do isooctano em 5 diferentes avanços de ignição. Para o ensaio com etanol hidratado são apresentadas as análises realizadas com 6 relações de compressão, 5 avanços de ignição e 5 relações ar-combustível, onde todos os valores destes parâmetros em estudo abrangem faixas típicas de operação de motores comerciais. Os resultados indicam um menor ângulo de combustão para relações de compressão elevadas, condição de mistura ligeiramente rica e elevados avanços de ignição. / The flame speed propagation in Otto cycles engine is a conclusive fuel feature, whose knowledge has a fundamental importance for a better accuracy of the pair engine/fuel. The higher flame speed propagation enables a greater cylinder filling, which can also increase power with improvements in engine speed, as a result holding back the ignition advance. Thus, it will be necessary a lower negative work to compress the mixture already in combustion before the top dead center, then resulting a greater efficiency cycle. The flame speed propagation is highly influenced by the compression ratio, mixture condition and ignition advance. This thesis proposes to investigate the influence of these operational parameters over the flame speed propagation in a CFR engine [Cooperative Fuel Research]. In this way, the angle measurements are performed between the fuel ignition timing and the flame detection over the opposite edge of combustion chamber by a ionization sensor in a CFR engine, as well as the diagram work pressure versus volume, which allows the net work evaluation produced by cycles and available the high pressure value, the angle with this occurs, the mean effective pressure and the curve of mass fraction burned for each tease condition. It introduces the analysis of combustion duration variation as much MTBE as the isooctane in 5 distinct ignition advance for the hydratated ethanol testing are introduced analysis accomplished with 6 compression ratio, 5 ignition advances and 5 air/fuel ratio, whose parameters values studies incorporates typical operational ratios of commercial engines. The results indicated a low angular combustion duration for the higher compression ratio, slightly rich mixture condition and elevated ignition advance.

Abstract: Isobutylene is a high demand chemical that contributes to the production of fuel, plastic, and rubbers. It is produced industrially by different processes, as a byproduct of steam cracking of naphtha or a fluidized catalytic cracking or by isobutane dehydrogenation. Catalytic dehydrogenation of isobutane is in increasing importance because of the growing demand for isobutylene and the better economic advantage compared to other isobutylene production processes. Isobutane dehydrogenation is an endothermic reaction and to achieve good yields; it is preferred to work at higher temperatures. At these temperatures, carbon deposition leads to catalyst deactivation, which requires the catalyst to be regenerated on a frequent basis. Most of the current processes to produce isobutylene use either expensive platinum-based metal or toxic chromium-based catalysis. Hence, there is a demand to search for alternative catalysts that are a relatively cheap and non-toxic. To achieve this goal, Zirconia-supported Iron catalysts were prepared. To study the effect of active phase distribution, different iron loadings were tested for impregnation (3% to 10%) and co-precipitation (10%-20%). The catalysts show promising results that can achieve an isobutylene selectivity and yield of 91% and 31%, respectively, with isobutane conversion of 35%.

No description available.

No description available.

Methyl tert-butyl ether (MTBE) has been used as a gasoline additive to improve the combustion efficiency and to replace lead since 1978. It is the most commonly used oxygenate now due to its low cost, convenience of transfer, and ease of blending and production. MTBE has become a prevalent groundwater contaminant because it is widely used and it has been disposed inappropriately. MTBE has been demonstrated an animal carcinogen. The US Environmental Protection Agency (US EPA) has temporarily classified MTBE as a possible human carcinogen and has set its advisory level for drinking water at 20-40 µg/L based on taste and odor concerns. The Taiwan Environmental Protection Administration (TEPA) also classifies it as the Class IV toxic chemical substances. Currently, natural attenuation (NA) as well as natural bioremediation or enhanced bioremediation are attractive remediation options for contaminated sites due to their economic benefit and environmental friendly. In general, in situ microorganisms at the contaminated site play a very important role in site restoration. Although early studies suggested that the biodegradability of MTBE was not significant, recent laboratory and field reports reveal that MTBE can be biodegraded under aerobic and anaerobic conditions. In addition, evidences and some successful cases of MTBE attenuation have been reported that make natural attenuation a considerable remedial strategy. However, the biodegrading rate might decrease if the nutritional and physiological requirements are not met. Thus, it is important to assess the biodegradability of natural microorganisms under various site conditions to obtain optimal remedial conditions. Contributions of intrinsic biodegradation and other abiotic mechanisms to the removal and control of contaminants should also be evaluated to provide sufficient information for remedial option determination. Moreover, isolation and identification of the dominant native microorganisms will be helpful to following remediation tasks. In the first part of this study, microcosm study and microbial identification technologies (denaturing gradient gel electrophoresis, DGGE) were applied to assess the biodegradability of MTBE by indigenous microbial consortia and to identify the dominant microorganisms at a MTBE-contaminated site (Site A). In the second part of this study, thorough field investigations were performed to evaluate the occurrence of natural attenuation of MTBE at two MTBE-contaminated sites (Site A and Site B). In addition, a natural attenuation model, BIOSCREEN, was performed to assess the effectiveness of natural attenuation on MTBE containment. The main objectives of this study contained the following: (1)Evaluate MTBE biodegradability under different redox conditions by the indigenous microorganisms. (2)Determine the dominant native microorganisms in MTBE biodegradation for further application. (3)Assess the feasibility of using natural attenuation to control the MTBE plume. (4)Evaluate the contributions of intrinsic biodegradation patterns on natural attenuation processes by BIOSCREEN. Results from the microcosm study reveal that MTBE could be biodegraded by aquifer sediments without the addition of extra carbon sources under aerobic conditions. The production of tert-butyl alcohol (TBA), a degradation byproduct of MTBE, was detected. Complete removal of TBA was also observed by the end of the experiment. Results from aerobic microcosms study indicate that oxygen might be the major limiting factor of MTBE biodegradation at Site A. Thus, MTBE at this site could be removed via natural biodegradation processes with the supplement of sufficient oxygen. Microcosm study with extracted supernatant of aquifer sediments as the inocula show that the indigenous microorganisms were capable of using MTBE as the sole carbon and energy source. The calculated MTBE degradation rate was 0.597 mg/g cells/h or 0.194 nmole/mg cells/h. No MTBE removal was observed under various anaerobic conditions. Results suggest that aerobic biodegradation was the dominant degradation process and aerobic bioremediation might be a more appropriate option for the site remediation. According to the results of DGGE analysis, aerobic MTBE-biodegrading bacteria, Pseudomonas sp. and Xanthomonas sp., might exist at this site. Although results of microcosm study show that MTBE could not be degraded under anaerobic conditions, the microbial identification indicates that some novel anaerobic microbes, which could degraded MTBE, might be present at this site. In addition, anaerobic microbes caused the consumption of electron acceptors (e.g., nitrate, ferric iron) and removal of benzene, toluene, ethylbenzene, xylenes (BTEX), 1,2,4-trimethyl benzene (1,2,4-TMB), and 1,3,5-trimethyl benzene (1,3,5-TMB) (TMBs) in the anaerobic microcosms. These results also indicate that the potential of anaerobes activities was high at Site A. Based on the results from the field investigation, natural attenuation of MTBE was occurring at both sites. MTBE plume at Site B could be effectively controlled via natural attenuation processes. Nevertheless, MTBE plume at Site A has migrated to a farther downgradient area and passed the boundary of the site. Field investigation results indicate that the natural attenuation mechanisms of MTBE at both sites were occurring with the first-order attenuation rates of 0.0021 and 0.0048 1/day at Sites A and B, respectively. According to BIOSCREEN simulation, biodegradation was responsible for 78% and 59% of MTBE mass reduction at Sites A and B, respectively. The intrinsic biodegradation had significant contributions on the control of MTBE plumes. Moreover, the dilution and dispersion processes might be the major mechanisms for the attenuation of MTBE in the downgradient areas. However, results also reveal that intrinsic biological processes might still fail to contain the plume if the selected point of compliance is not appropriate. Results of this study suggest that natural attenuation might be feasible to be used as a remedial option for the remediation of MTBE-contaminated site on the premise that (1) detailed site characterization has been conducted, and (2) the occurrence and effectiveness of natural attenuation processes have been confirmed. Based on the results from the field investigation and laboratory microcosm studies, MTBE could be biodegraded by natural microbial populations at the studied sites under both aerobic and anaerobic conditions and natural attenuation would be applied as a remedial option at MTBE-contaminated sites. Results from this study would be useful in determining the favorable bioremediation conditions and designing an efficient and cost-effective bioremediation system such as monitored natural attenuation (MNA) or in situ or on-site MTBE bioremediation system for field application.

ABSTRACT KINETIC STUDIES FOR THE PRODUCTION OF TERTIARY ETHERS USED AS GASOLINE ADDITIVES Boz, Nezahat Ph. D., Department of Chemical Engineering Supervisor: Prof. Dr. Timur Dogu Co-supervisor: Prof. Dr. G&uuml / lSen Dogu June 2004, 174 pages In the present study, the kinetics studies for etherification reactions were investigated in detail. In the first phase of present study, different acidic resin catalysts were prepared by the heat treatment of Amberlyst-15 catalysts at 220&deg / C at different durations of time and also by the synthesis of sulfonated styrene divinylbenzene cross-linked resins at different conditions. A linear dependence of reaction rate on hydrogen ion-exchange capacity was in 2M2B+ethanol reaction. However, in the case of 2M1B+ethanol reaction hydrogen ion-exchange capacities over 2.8 meq.H+/g did not cause further increase in reaction rate, which was concluded to be majorly due to significance of diffusional resistances. DRIFTS experiments carried out with alcohols, isobutylene, isoamylenes and TAME (tert-amyl-methyl-ether) in a temperature range of 333-353 K supported a Langmuir-Hinshelwood type reaction mechanism involving adsorbed isoolefins molecules forming a bridged structure between &ndash / SO3H sites of the catalyst and adsorbed alcohol molecules. A rate expression derived basing on the mechanism proposed from the DRIFTS results gave good agreement with the published data. Reaction rate was found to give a sharp maximum at ethanol activity of around 0.1. The third phase of this work included evaluation of effective diffusivities and adsorption equilibrium constants of methanol, ethanol and 2M2B, in Amberlyst-15 from moment analysis of batch adsorber dynamic results. Models proposed for monodisperse and bidisperse pore structures were used for the evaluation of effective diffusivities. It was shown that surface diffusion contribution was quite significant. In the last phase of the work, a batch Reflux-Recycle-Reactor (RRR) was proposed, modeled and constructed to achieve high yields and selectivities in equilibrium limited reactions. The batch reflux recycle reactor was modeled by assuming plug flow in the reactor section, perfect mixing in the reboiler and vapor-liquid equilibria between the liquid in the reboiler and reactor inlet stream. In this system conversion values of isoamylenes reaching to 0.91 were achieved at 82&deg / C with almost 100% selectivity. Such conversion values were shown to be much higher than the corresponding equilibrium values that could be obtained in vapor phase fixed bed reactors. The activation energies evaluated in this system were found to be much less than the activation energies evaluated in the fixed bed reactor studies. This was concluded to be majorly due to the significance of transport resistant in the batch Reflux-Recycle-Reactor in which catalyst particles are partially wet. As a result of catalyst development, characterization, kinetic and reactor development studies carried out in this study, it was concluded that tert-amyl-ethyl-ether (TAEE) could be effectively produced and used as a gasoline blending oxygenate.

A study was conducted to evaluate the sorption characteristics of six disinfection byproducts (DBPs) on four sorbents. To investigate sorption of volatile organic compounds (VOCs), specially designed experimental batch and continuous flow modules were developed. The investigated compounds included: chloroform, 1,2-dichloroethane (DCE), trichloroethylene (TCE), bromodichloromethane (BDCM), methyl tertiary butyl ether (MTBE), bromate and bromide ions. Sorbents used included light weight aggregate (LWA), an inorganic porous material with unique surface characteristics, Amberlite® XAD-16, a weakly basic anion exchange resin, Amberjet®, a strongly basic anion exchange resin, and granular activated carbon (GAC). Batch experiments were conducted on spiked Milli-Q® and lake water matrices. Results indicate considerable sorption of TCE (68.9%), slight sorption of bromate ions (19%) and no appreciable sorption for the other test compounds on LWA. The sorption of TCE increased to 75.3% in experiments utilizing smaller LWA particle size. LWA could be a viable medium for removal of TCE from contaminated surface or groundwater sites. Amberlite® was found unsuitable for use due to its physical characteristics, and its inability to efficiently remove any of the test compounds. Amberjet® showed an excellent ability to remove the inorganic anions (>99%), and BDCM (96.9%) from aqueous solutions but with considerable elevation of pH. Continuous flow experiments evaluated GAC and Amberjet® with spiked Milli-Q® and tap water matrices. The tested organic compounds were sorbed in the order of their hydrophobicity. Slight elevation of pH was observed during continuous flow experiments, making Amberjet® a viable option for removal of BDCM, bromate and bromide ions from water. The continuous flow experiments showed that GAC is an excellent medium for removal of the tested VOCs and bromate ion. Each of the test compounds showed different breakthrough and saturation points. The unique design of the continuous flow apparatus used in the study proved to be highly beneficial to assess removal of volatile organic compounds from aqueous solutions.