In order to satisfy the global requirement for transport fuel sustainably, renewable liquid biofuels must be developed. Currently, two biofuels dominate the market; bioethanol for spark ignition and biodiesel for compression ignition engines. However, both fuels exhibit technical issues such as low energy density, poor low temperature performance and poor stability. In addition, bioethanol and biodiesel sourced from first generation feedstocks use arable land in competition with food production, and can only meet a fraction of the current demand. To address these issues it is vital that biofuels be developed from truly sustainable sources, such as lignocellulosic waste resources, and possess improved physical properties. To improve and control the physical properties of a fuel for specific application, one must be able to tailor the products formed in its production process. All studies within this thesis, therefore, have the aim of assessing the fuels produced for their variability in physical property, or the aim of directing the process considered to specific fuel molecules.In Chapter 2, spent coffee grounds from a range of geographical locations, bean types and brewing processes were assessed as a potential feedstock for biodiesel production. While the lipid yield was comparable to that of conventional biodiesel sources, the fatty acid profile remained constant irrespective of the coffee source. Despite this lack of variation, the fuel properties varied widely, presumably due to a range of alternative biomolecules present in the lipid. Though coffee biodiesel was produced from a waste product, the fuel properties were found to be akin to palm oil biodiesel, with a high viscosity and pour point. The blend level would therefore be restricted. In Chapter 3 the coffee lipid, as well as a range of microbial oils potentially derived from renewable sources were transformed into a novel aviation and road transport fuel through cross-metathesis with ethene. Hoveyda-Grubbs 2nd generation catalyst was found to be the most suitable, achieving 41% terminal bond selectivity under optimum conditions. Metathesis yielded three fractions: an alkene hydrocarbon fraction suitable for aviation, a shorter chain triglyceride fraction that upon transesterification produced a short chain biodiesel fuel, and a multifunctional volatile alkene fraction that could potentially have application in the polymer industry. Though there was variation for the road transport fuel fraction due to the presence of long chain saturates, the compounds fell within the US standard for biodiesel. The aviation fraction lowered the viscosity, increased the energy density, and remained soluble with Jet A-1 down to the required freezing point. Oleaginous organisms generally only produce a maximum of 40% lipid, leaving a large portion of fermentable biomass. In Chapter 4, a variety of ethyl and butyl esters of organic acids – potentially obtainable from fermentation – were assessed for their suitability as fuels in comparison to bioethanol. One product, butyl butyrate, was deemed suitable as a Jet A-1 replacement while four products, diethyl succinate, dibutyl succinate, dibutyl fumarate and dibutyl malonate, were considered as potential blending agents for diesel. Diethyl succinate, being the most economically viable of the four, was chosen for an on-engine test using a 20 vol% blend of DES (DES 20) on a chassis dynamometer under pseudo-steady state conditions. DES20 was found to cause an increase in fuel demand and NOx emissions, and a decrease in exhaust temperature, wheel force, and CO emissions. While fermentation is generally directed to one product, producing unimolecular fuels, they do not convert the entirety of the biomass available. An alternative chemical transformation is pyrolysis. In Chapter 5, zeolite-catalysed fast pyrolysis of a model compound representative of the ketonic portion of biomass pyrolysis vapour – mesityl oxide – was carried out. The aim of this study was to understand the mechanistic changes that occur, which could lead to improved bio-oil yields and more directed fuel properties of the pyrolysis oil. While HZSM-5 and Cu ZSM-5 showed no activity for hydrogenation and little activity for oligomerisation, Pd ZSM-5 led to near-complete selective hydrogenation of mesityl oxide to methyl isobutyl ketone, though this reduced at higher temperatures. At lower temperature (150-250 °C), a small amount of useful oligomerisation was observed, which could potentially lead to a selective pyrolysis oligomerisation reaction pathway.
|Date of Award
|29 Jan 2015
|Chris Chuck (Supervisor) & Christopher Bannister (Supervisor)