published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

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This thesis described the development of new catalytic system for the conversion of natural gas (methane) to liquid products such as methanol and formaldehyde. This technology can allow the exploitation of small and medium size gas fields without the need to build an expensive gas to liquid plants or long pipelines. The technology is based on a concept of non-separating membrane reactor where an inorganic membrane paper serves as a catalyst support through which a reaction mixture is flowing under mild conditions and short residence times.

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Dairy cattle make a significant contribution to global methane emissions. Milking cows in the UK make up about a fifth of the total cattle population, with Holstein-Friesian cows being the most common breed. Investigating ways to minimise methane, a potent greenhouse gas (GHG) produced by dairy cows from enteric fermentation and manure, has gained importance in recent years due its role in climate change. Currently, GHG emissions from UK dairy farming are predicted using the Intergovernmental Panel on Climate Change (IPCC) Tier II methodology. The IPCC Tier II methodology and statistical prediction equations from the literature were evaluated for their ability to reliably model methane output using data from the Langhill Holstein-Friesian experimental herd. The Langhill dairy herd is on a long-term breeding and feeding systems experiment, and cows are on average 88% North American Holstein genes. The production systems within the herd represent a range of dairy systems that may be found commercially. Therefore, production values were assumed to be representative of those that could be found in the commercial Holstein-Friesian population, so factors affecting system methane emissions and appropriate mitigation options could be investigated. Prediction equations using dry matter (DM) intake and gross energy intake as input values were the most appropriate equations for reliably estimating daily enteric methane output. However, if DM intake values are not available, the IPCC Tier II method was found to provide a suitable prediction of methane emissions over a cow‘s lactation and lifetime. This study found that GHG emissions from enteric fermentation and manure, expressed as carbon dioxide equivalents (CO2-eq.), account for about 66% of dairy system CO2-eq. emissions, with enteric methane output being the main contributor (34% of system CO2-eq. emissions). Breeding for increased kilograms of milk fat plus protein production was shown to help reduce dairy system methane emissions. Cows of predominantly North American Holstein genes in this study produced more milk when fed a diet with a low proportion of forage and had lower GHG emissions and land requirement per kilogram energy corrected milk than similar cows fed a diet with a higher proportion of forage. Strategies to mitigate GHG emissions (including methane) and the environmental impact of dairy systems should seek to select animals that better utilise their feed intake to meet their genetic potential for milk production.

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.