Master's thesis. / Format: PDF. Bibl.

Three synthetic methods have been explored for the preparation of several novel boron-substituted amidinates and guanidinates. The extension of heterocumulene insertion chemistries to boron-aryl, boron-metallocene and boron-transition metal moieties has also been achieved and the mechanism of such insertions is addressed via density functional theory modeling techniques. The reactivity of these complexes is also explored, mainly through halide abstraction methodologies to generate boron cations, which are potent Lewis Acids and may be useful in promoting organic transformations or in the polymerization of ethylene. The synthesis and characterization of the elusive monomeric low valent carbenoid boron(I), a compound with a formal lone pair located upon the boron center, has been lacking. The suitability of the guanidinate ligand system to support such a species is also discussed and a combined experimental and theoretical approach to this highly topical problem is also presented. Thirdly, the use of photovoltaics (devices which convert solar energy directly into electricity) as an alternative source of energy outwith fossil fuel technologies is a rapidly growing area of interest. Initial efforts to use a novel approach, which incorporates inorganic nanocrystals wired into a conducting polymer matrix, are also presented. Successful synthetic approaches to the gallium, aluminum and indium monomeric precursors suitable for electropolymerization were developed. These compounds proved to be effective starting points for the generation of conducting polymers with embedded III/VI (Ga₂S₃) nanocrystals with further studies currently underway as to their III/V (InP, GaAs) compatriots. Finally, a retrospective of projects that may best be described in terms of the moniker "Loose Ends and Future Directions" will be presented. The aim of which will be to serve as a useful guidepost for further studies in the fields and topics discussed. / text

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The modern concept of “biorefinery” is dominantly based on chemical pulp mills to create more value than cellulose pulp fibres, and energy from the dissolved lignins and hemicelluloses. This concept is characterized by the conversion of biomass into various bio-based products. It includes thermochemical processes such as gasification and fast pyrolysis. In thermo-mechanical pulp (TMP) mills, the feedstock available to the gasification-based biorefinery is significant, including logging residues, bark, fibre material rejects, bio-sludges and other available fuels such as peat, recycled wood and paper products. On the other hand, mechanical pulping processes consume a great amount of electricity, which may account for up to 40% of the total pulp production cost. The huge amount of purchased electricity can be compensated for by self-production of electricity from gasification, or the involved cost can be compensated for by extra revenue from bio-transport fuel production. This work is to study co-production of bio-automotive fuels, bio-power, and steam via gasification of the waste biomass streams in the context of the mechanical pulp industry. Ethanol and substitute natural gas (SNG) are chosen to be the bio-transport fuels in the study. The production processes of biomass-to-ethanol, SNG, together with heat and power, are simulated with Aspen Plus. Based on the model, the techno-economic analysis is made to evaluate the profitability of bio-transport fuel production when the process is integrated into a TMP mill.The mathematical modelling starts from biomass gasification. Dual fluidized bed gasifier (DFBG) is chosen for syngas production. From the model, the yield and composition of the syngas and the contents of tar and char can be calculated. The model has been evaluated against the experimental results measured on a 150 KWth Mid Sweden University (MIUN) DFBG. As a reasonable result, the tar content in the syngas decreases with the gasification temperature and the steam to biomass (S/B) ratio. The biomass moisture content is a key parameter for a DFBG to be operated and maintained at a high gasification temperature. The model suggests that it is difficult to keep the gasification temperature above 850 ℃ when the biomass moisture content is higher than 15.0 wt.%. Thus, a certain amount of biomass or product gas needs to be added in the combustor to provide sufficient heat for biomass devolatilization and steam reforming.For ethanol production, a stand-alone thermo-chemical process is designed and simulated. The techno-economic assessment is made in terms of ethanol yield, synthesis selectivity, carbon and CO conversion efficiencies, and ethanol production cost. The calculated results show that major contributions to the production cost are from biomass feedstock and syngas cleaning. A biomass-to-ethanol plant should be built over 200 MW.In TMP mills, wood and biomass residues are commonly utilized for electricity and steam production through an associated CHP plant. This CHP plant is here designed to be replaced by a biomass-integrated gasification combined cycle (BIGCC) plant or a biomass-to-SNG (BtSNG) plant including an associated heat & power centre. Implementing BIGCC/BtSNG in a mechanical pulp production line might improve the profitability of a TMP mill and also help to commercialize the BIGCC/BtSNG technologies by taking into account of some key issues such as, biomass availability, heat utilization etc.. In this work, the mathematical models of TMP+BIGCC and TMP+BtSNG are respectively built up to study three cases: 1) scaling of the TMP+BtSNG mill (or adding more forest biomass logging residues in the gasifier for TMP+BIGCC); 2) adding the reject fibres in the gasifier; 3) decreasing the TMP SEC by up to 50%.The profitability from the TMP+BtSNG mill is analyzed in comparison with the TMP+BIGCC mill. As a major conclusion, the scale of the TMP+BIGCC/BtSNG mill, the prices of electricity and SNG are three strong factors for the implementation of BIGCC/BtSNG in a TMP mill. A BtSNG plant associated to a TMP mill should be built in a scale above 100 MW in biomass thermal input. Comparing to the case of TMP+BIGCC, the NR and IRR of TMP+BtSNG are much lower. Political instruments to support commercialization of bio-transport fuel are necessary. / Gasification-based Biorefinery for Mechanical Pulp Mills

Thesis (M.S.)--Ohio University, November, 1998. / Title from PDF t.p.

Thesis (Ph. D.)--University of New South Wales, 1999. / Also available online.

Thesis (Ph. D.)--University of Hong Kong, 2008. / Also available in print.