The study of the aromatisation of methane was conducted at 750oC over metalimpregnated H-ZSM-5 catalysts with a feed flow rate of 13 ml/min and the composition of the feed was 90% methane balance argon. Typical products that were detected from the outlet stream were ethene, ethane, benzene and toluene. The amount of coke produced was determined by using 10% argon as an internal standard. The effects of different parameters such as the type of the support material, the molybdenum content, the %XRD crystallinity and SiO2/Al2O3 ratio of H-ZSM-5, the reaction temperature, the feed flow rate, the type of the molybdenum precursor, the catalysts preparation method, the addition of dopants, silanation and the regenerability of the catalysts were investigated. The results obtained showed that H-ZSM-5 was a better support for the preparation of catalysts used for the aromatisation of methane. Mo/H-ZSM-5 catalysts were more active when the molybdenum loading was between 2 and 4 wt% and loadings higher than 4% led to lower activities. The lower activities observed at higher molybdenum loadings was related to the poor dispersion and decrease in the pore volumes and surface areas observed due to the formation of MoO3 crystallites. Furthermore, the zeolite structure collapsed under the reaction conditions when the molybdenum loading was more than 4 wt%. The study showed that the conversion of methane increased linearly with increasing reaction temperature and the apparent activation energy of the reaction was found to be 64.5 kJ/mol. The results of the effect of the %XRD crystallinity of H-ZSM-5 on the performance of H-ZSM-5 catalysts showed that 2%Mo/H-ZSM-5 catalysts were more active when the crystallinity of the zeolite was between 50 and 70%. The conversion of methane decreased with an increase in the SiO2/Al2O3 ratio of H-ZSM-5. Higher aromatisation activities were observed when the SiO2/Al2O3 ratio of H-ZSM-5 was iii 60. The type of the molybdenum precursor used in the preparation of 2%Mo/HZSM- 5 catalysts did not have a significant influence on the conversion of the catalysts, but higher selectivities for aromatics were observed when ammonium heptamolybdate was used as a source of molybdenum. The catalysts prepared by physical mixing of MoO3 and H-ZSM-5 catalysts were more active than those prepared by impregnation with solutions of ammonium heptamolybdate. The presence of dopants such as boron, silver and alkali metal ions (Li+, Na+ and K+) in 2%Mo/H-ZSM-5 catalysts was also investigated. Boron (0.05-0.2 wt%) did not affect the conversion level of the catalysts but changed their selectivity properties. The selectivity for C2 hydrocarbons increased with boron content, while the selectivity for aromatics decreased. The addition of silver ions (0.5 wt%) significantly improved the conversion of the catalysts. This was attributed to the enhancement of the acvidity of the catalysts upon addition of silver ions which was observed by temperature programmed desorption of ammonia and pyridine adsorption studies of the infrared spectra of the catalysts. The addition of alkali metal ions in the Mo:Metal ratio of 0.5 led to decreased catalytic activities, due to the lowered acidities of the catalysts. The silanation of H-ZSM-5 improved the conversion of methane but lowered the selectivity for aromatics. A comparative study of the W-based and Mo-based catalyst at equivalent molar contents showed that molybdenum-based catalysts were more active than tungsten based catalysts. The study also showed that the catalytic performance of 2%Mo/H-ZSM-5 catalysts could be regenerated to appreciable levels by treatment of the catalysts in air at 600oC. The possibility of using Mo/H-ZSM-5 catalysts for the aromatisation of propane was also evaluated at 530oC, with consideration of three variables, namely, the molybdenum loading, the reaction temperature and %XRD crystallinity. The results indicated that impregnation H-ZSM-5 catalysts with molybdenum led to lower iv propane aromatisation activities. This lower activity was attributed to the lower Brønsted acid sites in the Mo/H-ZSM-5. The activities of the catalysts could be improved by operation at higher temperatures, but the rate of deactivation was also improved at higher temperatures. In line with the observations from the conversion of methane, higher activities were observed when the %XRD crystallinity of the catalyst was 61%.

No description available.

Lakes are a significant source of the powerful greenhouse gas methane (CH4) globally. Methaneis produced through microbial processes in anoxic sediments. Methane emission from lakes ishighly variable in space and time. Consequently, is it difficult to predict the methane production rate and at present time it cannot be predicted from sediment characteristics. Therefore, methane production in the sediment of contrasting Swedish lakes was investigated, in order to find out if methane production rate can be related to sediment characteristics, and if a predictive model that recently was developed for Brazilian reservoirs is applicable to Swedish lakes. For this, sediment cores were collected from six lakes, differing in their sediment characteristics and geographical position as well as one river. The sediment cores were sliced into one centimetre thick layers. The different layers were incubated and methane production rate was measured. The sediment layers were also analysed for water content, median grain size, total nitrogen and carbon content as well as age. The influence of sediment age and C:N ratio as predictors for methane production were tested with a mixed linear model and a non-linear model. Both models showed that age had a significant effect on methane production rate (p < 0.001). The C:N ratio also had a statistically significant effect on methane production rate only shown with the non-linear model, however this effect was weak. Applying the recently published predictive model for methane production rate in Brazilian reservoir sediments to this data from the Swedish lakes, provided a good prediction of methane production rate in the nutrient-rich Swedish lakes, however it overestimated the methane production rate of the humic-rich boreal lakes and sediment older than 50 years. In summary, a model using age as predicting factor was developed fitting all the studied Swedish lakes. In addition, the predictive model developed in Brazilian reservoirs for the methane production rate was valid only for the studied nutrient-rich Swedish lakes and the studied oligotrophic Swedish lakes.

With population growing every year, more and more people are looking for places to live. This can lead to construction of houses near and around landfills. As homes get closer to landfills, the odors these landfills produce become more of a problem, and lead to an increase in odor complaints. Modeling these odors and recommending odor buffer distances will help determine limits on how close to landfills new homes should be allowed. This should help reduce future odor complaints. To solve this problem one must accurately estimate odorous gas emissions from the landfill. Often odors can be indicated by methane emissions. A new technique using hundreds of ambient VOC concentrations, which are taken from landfills on a quarterly basis, was used to invert and solve the Gaussian dispersion equation for methane emissions. In this technique, Voronoi diagram theory was used to automatically locate numerous point sources for optimal positioning relative to receptors. The newly solved methane emission rates can now be input into a dispersion model, and the resulting methane concentrations used as surrogates for odors around the landfill. One of the most important steps in the analysis is to determine which model is best to use for odor modeling. There are many considerations that go into this decision, such as how much time it takes to run the model, how accurate the model is, and how easy the model is to use. Two current models CALPUFF and AERMOD were compared. In the modeling, methane was used as a surrogate for the odors. Since landfills handle many different combinations of waste, the type of odor may vary from landfill to landfill. In this test case, H2S was assumed to be the main contributor to the odor emitted from the landfill, and the H2S-to-methane ratio was used to estimate downwind H2S concentrations from the modeled methane concentrations. Once an air dispersion model is selected, it can be used to model odors and to develop a graphical screening method to show where these odors are most likely to occur and how strong they will be. This can be used to determine how close to a landfill homes can be built without having significant odor impacts bothering these new residents. Also, this tool can be used for improving landfill gas management. Several example scenarios include the possibility of not enough soil cover placed on the waste, leaks from an aging collection system, or cracks in the collection piping created by the settling of waste.

Advanced three-dimensional reservoir modeling was used to determine the optimum strategy for coalbed methane production in China's Qinshui Basin. Multiple completion strategies were analyzed for pre-mining methane drainage on the bases of economic, environmental, and mining-safety-based factors. Effective degasification in the Qinshui Basin is crucial to enhance the health and safety of the underground mining workforce and to decrease carbon dioxide equivalent greenhouse gas emissions. Active, large-scale degasification wells in the region include hydraulically stimulated vertical fracture wells and multilaterally drilled horizontal patterns, with the latter much less common. Reservoir modeling concludes that despite their limited implementation, horizontal coalbed methane drainage wells offer the benefits of faster reservoir depressurization, high gas production rates, and faster recovery times than traditional vertical fracture wells. Coupled with reservoir modeling results, discounted cash flow analyses show that high drilling density multilateral horizontal patterns are the most financially feasible degasification strategy in the Qinshui Basin, albeit a higher initial capital investment compared to traditional vertical fracture wells and lower drilling density horizontal patterns. Additionally, horizontal wellbore designs can be altered to account for varying permeability, enhancing the productivity of methane from reservoirs exhibiting permeability values less than 1 millidarcy. Furthermore, modeling suggests that proper orientation of select horizontal wellbore patterns is crucial to optimize recoverable reserves. Finally, a function was derived to represent the production rates of horizontal coalbed methane wells as a function of time. Analysis of the function's validity to actual production data and simulated production data suggest that it is most applicable in gassy coal seams up to 10 feet in thickness. The production rate curve was transformed to an analytical model, representing a function of well geometry and coal permeability as applied to other geological conditions of the Qinshui Basin. Scientific contributions associated with this research include: An in depth study of degasification associated with the Qinshui Basin's low permeability coals; The methodology for assessing environmental, safety and economic benefits of coal degasification; The relationship between lateral spacing and permeability to maintain substantial gas production rates; An improved production model to describe the entire producing period of coalbed methane wells. / Ph. D.

<p> The total scattering cross section of solid methane has been measured for temperatures in the range from 4.2°K to 95°K. An anomalous increase in the total scattering cross section was observed at temperatures below 5°K. The effect is ascribed to conversion between nuclear spin species. Such spin conversion had been indicated by specific heat and NMR measurements; the present results give an independent confirmation of this. Calculations of the equilibrium value of <I(I + 1)> at 4.2°K give values lower than those obtained in the NMR work. The specimens used in the present work come to spin equilibrium in times much less than 20 minutes. This is less than the value of 90 minutes for pure methane seen by NMR; however, very small amounts of oxygen impurity in the specimen are known greatly to decrease this time.</p> <p> An abrupt change in the total scattering cross section at the 20°K phase transition is explained by a change in the rotational freedom of the molecules to a more strongly hindered state below the phase transition. In the region above the transition, the Krieger-Nelkin approximation for the total cross section was fitted to the observed temperature dependence of the cross section, treating the effective mass as a free parameter.</p> / Thesis / Master of Science (MSc)

<p> The use of gamma radiation to initiate the iodination of methane in liquid phase was studied using a semi-batch technique whereby the methane was bubbling through a column of iodine solution in a reactor. Yields of CH3I and CH2I2 lower than 10% and G < 500 were obtained as contrasted with the 60% yield and G=7xl0^7 reported in the gas-phase reaction. In view of the propensity of the iodine as a radical scavenger and the endothermic nature of the reaction, various attempts to improve the low yields were carried out. Results are eiven that indicate the chances of achieving a laree G value for liquid-phase reaction are very low even if the operating conditions are optimized. </p> / Thesis / Master of Engineering (MEngr)

<p> We present a discussion of the application of group theory to the particular case of solid methane, in all its crystalline phases. </p> <p> We also employ the quantum mechanical mean approximation to derive the mean square angle of deviation of the methane free molecule. By means of group theory we derive the normal modes, the symmetry coordinates and the nuclear spin functions of methane, which may be found useful for many other purposes in the study of methane. Finally, using these results, we give a discussion of the infrared and Raman spectra based on group theory again, to explain the observed transitions of the methane molecule in its condensed phases. We conclude that the λ type transitional are caused by changes in molecular orientation. Phase I is probably disordered,while phase II has structure of symmetry D2d. Phase III (of CD4) is ordered but of lower symmetry and unclear structure. </p> <p> A possible explanation probably requires an arrangement having more molecules per unit cell than in phases I and II. </p> / Thesis / Master of Science (MSc)

The price fluctuation and depletion of crude oil have led to the fervent interest in finding alternatives that can satisfy our increasing need for energy. In the past decades, two primary approaches are seen as promising ways to remedy our dependence on crude oil: first, the use of natural gas, primarily methane, to produce high-value hydrocarbons, and second, the use of ammonia as a hydrogen carrier. In this dissertation, we used density functional theory (DFT) calculation and kinetic modeling to investigate methane activation and C-C coupling on WC as well as the ammonia decomposition over the CoNi alloy surface. From our methane conversion project, we investigated the reactivity of W-terminated WC(0001) and WC(112 ̅0) surface toward methane activation and conversion to produce C2 moieties using DFT. We first calculate the intermediates binding energies and activation and reaction energies of methane dissociation. We found that WC(112 ̅0) is better at dissociating the first C–H bond than WC(0001). Our results also indicate that the surface is likely populated by (CH)ads species. The mobility of (CH)ads species on both surfaces allows the possibility of C-C coupling, resulting in a precursor for higher hydrocarbon formation. Our results also demonstrate that the WC(0001) surface favors the production of the (C2H2)ads species, whereas the WC(112 ̅0) surface dissociates CHx completely, resulting in coke formation. Thus, methane dissociates readily on the WC surfaces whereas the formation of the C2 species is sensitive to the surface structure. The DFT study on ammonia decomposition has been performed in close collaboration with the experimental study. A highly active catalyst consisting of CoNi alloy nanoparticles well-dispersed on a MgO–CeO2–SrO mixed oxide support with potassium promotion exhibited a performance matching that of the Ru-based catalysts. Extensive characterization in combination with the DFT results revealed that the CoNi alloy surface and metal/oxide interfaces are the active sites for catalytic decomposition of ammonia. Moreover, the much improved catalytic activity stems mainly from the presence of interface where the recombinative desorption of nitrogen has been greatly enhanced. These have been demonstrated by examining the detailed elementary steps of ammonia decomposition on the Co, Ni, Co2Ni, CoNi2 (111) surfaces and at the CeO2/Co2Ni interface. We calculated the binding energies of intermediates and the activation energies of each elementary step in ammonia decomposition. We found that on the Co, Ni, Co2Ni, CoNi2 surfaces, N–N bond formation is the rate-determining step, with the CoNi alloy surfaces having a lower activation energy than the pure metal surfaces. Over the CeO2/Co2Ni interface, however, N–H bond dissociation becomes rate-determining. The high catalytic activity at the CeO2/Co2Ni interface originates from the localized charge polarization due to alloying and the presence of the oxide which drastically facilitates N2* formation. We then integrated the DFT-calculated adsorption and activation energies in the microkinetic modeling of ammonia decomposition on the Co, Co2Ni, CoNi2, and Ni surfaces, focusing on the alloying effect. Two cases were investigated: ammonia decomposition in the 1) absence and 2) presence of product re-adsorption. In both cases, we determined the turnover frequencies, the apparent activation energies, the steady-state coverages, the degree of rate control, and the reaction orders. Our results show that in both cases, the alloys have higher catalytic performance than the pure metals. We also found that as the temperature increases, ammonia decomposition switches from being limited by N–N (and N–NH) bond formation to N–H bond dissociation. This change of mechanism is predicted to occur at lower temperatures on the alloy surfaces. In the case of hydrogen re-absorption, the surface H* adatom retards the last N–H bond-breaking step, resulting in the high coverage of NH* species on the surfaces, making N–NH coupling an alternative pathway for N2 formation. Furthermore, our microkinetic results show that alloying Ni with Co reduces the effect of hydrogen inhibition at high hydrogen partial pressures. In summary, this dissertation provides information for the design of efficient catalysts toward methane conversion and ammonia decomposition.

As societies around the world become increasingly more dependent on fossil based fuels, the need to investigate alternative fuel sources becomes more pressing. Renewable, biomass-based carbon sources obtained from the biosphere can be gasified to produce synthesis gas, which can in turn be fermented to produce fuel-grade ethanol. A byproduct of ethanol production via fermentation is acetic acid. An optimized ethanol fermentation process should produce a wastewater stream containing less than 2 g/L of acetic acid. This is not enough acid to justify recovery of the acid; however it is a high enough concentration that treatment of the stream is required before it can be discharged. The purpose of this research was to convert the acetic acid into biogas, producing a twoold result: removal of the acid from the wastewater stream and the production of methane, which is a valuable source of energy. Microorganisms known as methanogens will consume acetic acid to produce methane and carbon dioxide under anaerobic conditions. The goal of this research was to optimize methane production from the wastewater stream discharged from an ethanol to syngas facility. Sludge containing methanogenic organisms was obtained from the anaerobic digester of a wastewater treatment facility and used as inoculum in batch reactors containing a synthetic acetic acid solution. Variables such as the type and amount of supplied nutrients, acid concentration, pH, cell acclimation, oxygen exposure, headspace gas composition, and agitation rate were examined. The effects of these parameters on the amount of biogas produced and acetic acid degraded were used to evaluate and optimize reactor performance. Additional experimentation further evaluating methanogenesis at low pH was also conducted using a laboratory scale semi-continuous fermentor. Finally, advanced analytical techniques were used to evaluate changes in organism population with respect to changes in reactor operational parameters. The results of this research were used to estimate kinetic parameters, develop different full-scale reactor design models, and estimate the both the cost of wastewater treatment as well as the value of the methane produced.