Abstract Biological oxidation of methane is and important constraint on the emission of this gas from areas, such as landfills to the atmosphere. We studied the effect of covering soils on methane emission in landfill assimilation. Microbial evaluation was done on virgin soil and later on soils used as covering material. This soil was later treated differently to see different effects that has on methane emission. Treatments applied were addition of compost in soil, moistured soil with methanotroph culture instead of water. Although methane was produced from the landfill, it was not as documented between 45 and 50%. We got between 6 and 18% production. In all the soils tested the uncultivated soil had the minimal emission as it emitted 0% methane. Sand, however, had some oxidation effect. The problem was that it is porous therefore gas migration is not restricted. This shows that the oxidative bacteria are available naturally is soils, but gets abandoned as the conditions favours their growth. The treatments done to soils had little effect as methane oxidation was not influenced or altered. This can be liked into in details. There have been some good observations in the assimilated landfill. As the landfill was not controlled the pH dropped and this in return produced more hydrogen as compared to methane. With all the altered gas balance produced the leachate changed.

PhD - Science / Gold has been regarded as being inert and catalytically inactive for many years compared with for example the platinum group metals. However, for the past decade gold has attracted a growing attention as both a heterogeneous and homogeneous catalyst and it has been shown that it can catalyze a wide range of reactions such as oxidation, hydrogenation, reduction, etc. This project entails the synthesis, characterization and testing of a suitable gold catalyst for the oxidation of carbon monoxide (CO), and some hydrocarbons (methane). In this project 2 wt% Au/TiO2; Au/TiO2-ZrO2; Au/TiO2-CeO2 catalysts were prepared by both deposition-precipitation and co-precipitation methods. Different synthesis conditions such as pH, catalyst ageing, and catalyst pretreatment were investigated in order to find suitable conditions for the preparation of catalyst that would be more active at lower temperature range (25 oC – 100 oC). The techniques used for catalyst characterization include, TGA, XRD, BET, XPS, TPR, XANES, HRTEM etc. in order to elucidate the catalyst surface structure and its suitability in affecting adsorption and subsequently catalytic activity. Carbon monoxide and methane oxidation reactions were undertaken in a tubular glass flow reactor. It was observed that when gold is well dispersed on a suitable support, it can catalyze total oxidation of CO at room temperature, provided that certain preparation and pretreatment conditions are followed. An uncalcined catalyst was found to be more active than the catalyst calcined at higher temperatures. This is due to the agglomeration of gold particles on the surface of the support according to our High Resolution Transmission Electron Microscopy results. With Mössbauer spectroscopy, it was observed that the addition of the second support metal oxide such as zirconia resulted in the decrease in agglomeration of gold particles. In such iv catalysts, a considerable amount of ionic species were preserved even after calcination at 400 oC resulting in the higher activity. With Au/TiO2, a batch of uncalcined catalyst dried at 120 oC overnight was leached with cyanide to remove the bulk metallic gold particles, supposedly leaving mostly ionic, small, and well dispersed gold particles and the activity of such leached catalyst was higher than that of the unleached sample. Methane oxidation was found to be very difficult compared with carbon monoxide, and only 8% conversion was achieved at 450 oC whereas a total CO oxidation was achieved at lower temperatures with the same catalyst. It is conclusive that small, ionic well dispersed gold species are necessary for CO oxidation and the adsorption and the active sites for this reaction may be different from those involved in methane oxidation.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. Johannesburg, 1996 / In present thesis the results of a study of the combined action of a solid catalyst and a gas-phase inintiator, hydrogen peroxide, in the methane partial oxidation and oxidative coupling reactions are presented. [Abbreviated Abstract. Open document to view full version] / MT2017

The search for an alternative clean and renewable energy source has become an urgent matter. One such energy-saving technology is a fuel cell; it uses fuel as the source of energy to produce electricity directly and the byproducts formed are not as voluminous and environmentally harmful. The conventional low temperature fuel cells use hydrogen as the fuel which is produced from conventional fuels via reforming. However, developing reformers for hydrocarbon fuels requires AN understanding of the fundamental mechanisms and kinetics studies. In this study, simple hydrocarbon fuel, namely methane, in external reforming or internal reforming within a solid oxide fuel cell has been studied because of its importance and with the hope that it will ultimately lead to an understanding of reforming of higher hydrocarbons, such as logistic fuels like JP-8. For this purpose, methane was used the starting point and building block for the progressive understanding of reforming of complex hydrocarbons. Methane steam reforming (MSR), CH4 + 2H2O = CO2 + 4H2 is, in fact, the most common method of producing commercial bulk hydrogen along with the hydrogen used in ammonia plants. United States alone produces 9 million tons of hydrogen per year. The overall MSR reaction CH4 + 2H2O = CO2 + 4H2 is in fact composed of two reactions, the water gas shift reaction, CO + H2O = CO2 + H2, which has recently been investigated by a former Ph.D. student in our group, Caitlin Callaghan. Here, the first reaction CH4 + H2O = CO + 3H2, i.e., methane reforming, is analyzed using a reaction route network approach to obtain the overall methane steam reforming network and kinetics. Kinetics providing detailed information of elementary reaction steps for this system, namely micro-kinetics, has not yet been fully addressed. Employing the theory of Reaction Route Network Theory, recently developed by Fishtik and Datta, and using the Unity Bond Index-Quadratic Exponential Potential (UBI-QEP) method of Shustorovich to predict elementary step kinetics coupled with transition-state theory, a detailed microkinetic model of steam and dry reforming of methane has been developed for Rh(111) and Ni(111) in this thesis. While there is extensive literature on it, the standard reference on the mechanism and kinetics of MSR is that of Xu and Froment, who proposed a 13 step mechanism. Based on the assumption of rate limiting steps for these overall reactions, Xu and Froment derived rate expressions for overall kinetics with fitted parameters. Here a more detailed micro-kinetic model of steam reforming of methane has been developed by adding 3 steps pertinent to carbon formation on the catalyst to Xu and Froment's mechanism. The complete set as well as the dominant reaction routes has been identified. This was accomplished first by enumerating the list of reaction routes and drawing this network. A program was written in Maple and was used to assist in creating the list of full routes, empty routes and intermediate nodes. This program reduces the amount of repetitive work that was needed in an earlier Matlab program when computing the list. After drawing the complete reaction network it was than converted into an equivalent electrical circuit and Multisim analysis was performed. Further, the resistances of various reaction steps were compared. From the reduced graph, it was determined that reaction steps pertaining to desorption of carbon dioxide, i.e., step s4, and intermediate methylene forming intermediate methylidyne, s11, are the rate limiting steps. Further, through simulation with Multisim, it was determined that in fact only 2 overall reactions are needed. Adding a third overall reaction results in a nodal balance error. A rate expression was developed based on assuming the above two rate determining steps, with remaining steps at pseudo equilibrium along with the quasi-steady state approximation. The rate expression however produced a substantial error in conversion when compared to the overall microkinetic model. In addition to computing the micro-kinetic model, experimental work for methane steam reforming was conducted. A steam to carbon ratio of 2:1 was fed to the packed bed reactor, where experimental conversion data were obtained. These data points for Ni and Rh catalyst were plotted against the model to see how well the simulation predicted the experimental results. Reasonable agreement was obtained.

The aim of this thesis is to develop a set of intermolecular potentials that enable the study of nucleation or decomposition of methane hydrates. The potentials are developed for water, methane, and the water-methane pair by fitting to SAPT(DFT) reference energies. The first set of potentials developed differ from recent polarisable models in that they have rank 4 ISA multipoles, rank 3 anisotropic polarisabilities, rank 3 isotropic dispersion, and anisotropic exchange-repulsion terms. These potentials are validated based on the structures and energies of small clusters and second virial coefficients. The potentials are then significantly simplified for use in MD simulations with DL_POLY4. Simplifying the methane potential makes it difficult to fit simultaneously the global minimum dimer and a set of randomly generated dimers used as reference energies. Several methods are tested to account for polarisation in water within the limitations of DL_POLY and it is found that for MD simulations good results can be attained by increasing the charge values to match the multipole moments of a water molecule in a dielectric. Simulations are carried out for liquid water, ice Ih, and methane gas to validate the new models. The models developed are compared in MD simulations with TIP4P/Ice and the United Atom Methane (UAM) model in simulations of sI methane clathrate; both under stable conditions and while undergoing decomposition at different temperatures. It is found that the melting behaviour differs according the methane- and water-methane interactions; the behaviour of methane under clathrate decomposition using either methane model is discussed.

This work takes a closer look at ceria catalyst synthesis through micelle self-assembly. We compare surfactants, precursors, solvent systems, and doping. The surfactants are the building blocks upon which the ceria can crystallize. The samples are calcinated to test their thermal stability. Characterization is performed using pXRD as well as physisorption. The samples that exhibited a higher thermal stability were characterized to have a high surface area as well as low fluctuations in crystallite size, pore volume, and pore size. Ceria synthesized with cerium (III) nitrate hexahydrate and CTAB in a water:ethanol mixture using sodium hydroxide showed to be the most effective at providing a thermally stable product. Doping the catalyst with titanium increased the thermal stability significantly. Select samples were run in a variety of fuel to oxygen ratios to determine the best conditions in which we could perform partial methane oxidation to recuperate hydrogen gas. Most of the experiments show oxygen depletion with minor changes in other gas levels indicating that there is no oxidation occurring. Curiously the oxygen levels do decrease. There is a possibility that there is a reaction occurring initially at room temperature and being exacerbated with further temperature increase.

Aerobic methanotrophs (MOB) are a functional group of proteobacteria that use methane as their only energy and carbon source. Phylogenetically, such methanotrophs are affiliated with present alpha and gamma proteobacteria. Methanotrophic microorganisms play an essential role in the methane cycle, since they to a great extent reduce potential methane emissions to the atmosphere. In stratified lakes the aerobic methanotrophs are commonly present at the oxic-anoxic interfaces. This study aims to identify the environmental factors that could regulate the distribution of aerobic methanotrophs in the water column of freshwater lakes as well to assess whether a vertical community structure exists there. Lakes Erken and Tämnaren located in central Swedenwere studied using molecular analysis and environmental data. Aerobic methanotrophs were detected throughout the water column of Lake Erken. Two types of methanotroph communities were identified, with distribution patterns that appeared to be correlated to levels of methane in the water. Furthermore one of these communities feature changes in the relative abundance of its member populations along a depth gradient suggesting further differentiation along chemical gradients in the hypolimnion. Sequencing of pmoA amplicons revealed only members of the gamma proteobacteria methanotrophs. Also two novel operational taxonomic units were identified. Methanotrophs communities between Tämnaren and Erken also differ. Together these results indicate the existence of distribution patterns in methanotroph freshwater communities.

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Estimation of viscosities of naturally occurring petroleum gases provides the information needed to accurately work out reservoir-engineering problems. Existing models for viscosity prediction are limited by data, especially at high pressures and high temperatures. Studies show that the predicted viscosities of natural gases using the current correlation equations are about 15 % higher than the corresponding measured viscosities at high pressures and high temperatures. This project proposes to develop a viscosity prediction model for natural gases at high pressures and high temperatures. The project shows that commercial gas viscosity measurement devices currently available suffer from a variety of problems and do not give reliable or repeatable results. However, at the extremely high pressures encountered in high pressure and high temperature reservoirs, the natural gases consist mainly of methane as the hydrocarbon constituent and some non-hydrocarbon impurities. Available viscosity values of methane were used in the development of a correlation for predicting the viscosities of naturally occurring petroleum gases at high pressures and high temperatures. In the absence of measurements, this correlation can be used with some confidence.

Thesis (Ph. D.)--Lehigh University, 2002. / Includes vita. Includes bibliographical references (leaves 94-97).