Biodiesel is one of the most widely used biofuels in the world, due in part to its simplicity of production, compatibility with existing engines, and reduction of green house gas emissions. However, technical difficulties with biodiesel include: (1) the need of highly refined oil for ASTM compliance, (2) incompatibility with the petroleum-diesel pipeline distribution system, and (3) a relatively small inventory of expensive feedstocks. Issues (1) and (2) could be overcome by the production of biofuels using chemical processes associated with petroleum refining. Catalytic lipid cracking could result in green diesel, a fuel chemically similar to conventional diesel but derived from a clean renewable feedstock. The impact of phosphorus poisoning on catalytic cracking of lipids has been studied in this work using both homogeneous and heterogeneous catalysts. Catalytic cracking of model lipids was shown to occur in a homogeneous liquid phase with triflic acid, a superacid 100 times more acidic than sulfuric acid. Products obtained from the reaction were heavily oxygenated and generally unsuitable for fuel use, suggesting the need for heterogeneous catalytic cracking. Reaction kinetics show a high linear dependence on Brönsted system acidity, with an overall reaction order of 3. The affect of phosphorus on heterogeneous acid cracking was then studied. Since lipid feedstocks contain small amounts of phospholipids knowledge of the interactions between phospholipids and zeolites is crucial to a system-wide understanding of the lipid cracking process. Phosphorus-containing compounds were used to poison ZSM-5 (a solid zeolite catalyst) in order to simulate the cracking of phospholipids. Model compounds were then cracked over the poisoned zeolite, with differences in product distribution and kinetics based on phosphorus loading recorded. It was shown that phosphorous has a dramatic effect on both conversion and product distribution of cracking reactions. It is believed that phosphorous binds irreversibly to heterogeneous active sites, causing the majority of deactivation. To address the issue of limited feedstock availability, research was also undertaken to find new lipids sources for biofuel use. It was determined that lipids extracted from microorganisms grown in a municipal wastewater treatment system could be suitable. However, any phosphorous must be removed before catalytic cracking of the extracted lipids.

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The energy security and climate change risks of fossil fuel consumption have stimulated interest in developing renewable energy sources. Canada’s vast biomass potential is an attractive local resource but high transportation costs are a barrier to implementation. This study assesses how transformative systems can enable large-scale bioenergy production through integration with existing transportation corridors and fossil fuel infrastructure. Potential bioenergy corridors include the network of natural gas pipelines and the Great Lakes St. Lawrence Seaway (GLSLS). Sustainable lignocellulosic biomass production integrated with traditional food and fibre production was assumed to occur on 196 Mha of land within 100 km of pipelines. Conservative (81 Mt of dry biomass per year) and aggressive (209 Mt) scenarios were investigated for converting biomass to synthetic natural gas (SNG) via gasification, methanation, and upgrading, yielding enough pipeline-quality gas to meet 20% to 60% of Canada’s current needs. A systems analysis approach was used to calculate bioSNG life-cycle emissions of 15 to 18 kgCO2e GJ-1, compared to 68 or 87 for conventional or liquefied natural gas, respectively. Production costs ranged from $16 to $20 GJ-1, which were high compared to regional gas prices ($5 to $10 GJ-1). The biomass potential on 125 Mha of land area within 100 km of the Canadian portion of the GLSLS and railway lines ranged from 36 to 80 Mt(dry) per year, which was enough to displace coal-fired power in Ontario plus produce 1.6 to 11 billion L of green diesel that could offset 14% to 96% of fossil diesel in GLSLS provinces. Life-cycle emissions ranged from 110 to 130 gCO2e kWh-1 for biopower (compared to 1030 for coal) and 20 to 22 kgCO2e GJ-1 for green diesel (compared to 84 for conventional diesel). Cost estimates ranged from $130 MWh-1 for biopower (compared to an average market power price of $54 MWh-1) and $28 to $36 GJ-1 for green diesel (compared to $16 to $24 GJ-1 for diesel). The auxiliary benefits (energy security, climate change, air quality, and rural development) were seen as justification for supportive bioenergy policies. / Thesis (Master, Environmental Studies) -- Queen's University, 2008-12-09 15:24:18.389

Renewability and the carbonaceous basis of biomass provide potential for both energy and chemical production in biorefineries in a fashion similar to crude oil refineries. Biorefineries are envisaged as having a key role in the transition to a more sustainable industry, especially as a means to mitigate greenhouse gas (GHG) emissions. A biorefinery is a concept for the flexible, efficient, cost-effective and sustainable conversion of biomass through a combination of process technologies into multiple products. This implies that biorefineries must be integrated through designs that exploit the interactions between material and energy streams. The wide range of possibilities for biomass feedstock, processes and products poses a challenge to biorefinery design. Integrating biorefineries within evolving economic and environmental policy contexts requires careful analysis of the configurations to be deployed from early in the design stage. This research therefore focuses on the application and development of methodologies for biorefinery design encompassing process integration tools, economic and environmental sustainability analyses together. The research is presented in the form of papers published or submitted to relevant peer-reviewed journals, with a preamble for each paper and a final synthesis of the work as a whole. In a first stage, mass pinch analysis was adapted into a method for integration ofbiorefineries producing bioethanol as a final product and also utilising bioethanol asa working fluid within the biorefinery. The tool allows targeting minimum bioethanol utilisation and assessing network modifications to diminish revenue losses. This new application could stimulate the emergence of similar approaches for the design of integrated biorefineries. The thesis then moves to combine feedstock production models, process simulations in Aspen Plus® and process integration with LCA, to improve energy efficiency and reduce GHG emissions of biorefineries. This work, presented via two publications covering wheat to bioethanol and Jatropha to biodiesel or green diesel, provided evidence of the benefits of biorefinery integrationfor energy saving and climate change adaptation. The multilevel modelling approach is then further integrated into a methodologydeveloped for the combined evaluation of the economic potential and GHG emissions saving of a biorefinery from the marginal performances of biorefineryproducts. The tool allows assessing process integration pathways and targeting forpolicy compliance. The tool is presented via two further publications, the first drawing analogies between value analysis and environmental impact analysis inorder to create the combined Economic Value and Environmental Impact (EVEI)analysis methodology, the second extending this to demonstrate how the tool canguide judicious movement of environmental burdens to meet policy targets. The research embodied in this thesis forms a systematic basis for the analysis andgeneration of biorefinery process designs for enhanced sustainability. The toolspresented will facilitate both the implementation of integrated biorefinery designsand the cultivation of a community of biorefinery engineers for whom suchintegrated thinking is their distinctive and defining attribute.

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 Geraldo Eduardo da Luz Junior_TESE.pdf: 1318067 bytes, checksum: bc521809cc7c08b9ef99f31a1034f3a2 (MD5) Previous issue date: 2010-04-26 / In order to obtain a biofuel similar to mineral diesel, lanthanum-incorporated SBA- 15 nanostructured materials, LaSBA-15(pH), with different Si/La molar ratios (75, 50, 25), were synthesized in a two-steps hydrothermal procedure, with pH-adjusting of the synthesis gel at 6, and were used like catalytic solids in the buriti oil thermal catalytic cracking. These solids were characterized by X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), infrared spectroscopy (FTIR), nitrogen porosimetry and ethanol dehydration, aiming to active sites identify. Taken together, the analyses indicated that the synthesis method has employed to obtain materials highly ordered mesostructures with large average pore sizes and high surface area, besides suggested that the lanthanum was incorporated in the SBA-15 both into the framework as well as within the mesopores. Catalytic dehydration of ethanol over the LaSBA-15(pH) products has shown that they have weak Lewis acid and basic functionalities, indicative of the presence of lanthanum oxide in these samples, especially on the La75SBA-15(pH) sample, which has presented the highest selectivity to ethylene. The buriti oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ?C in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. One the other hand, OL coming from second ones, called green diesel (GD), have presented low acid index, particularly that one obtained from the thermal catalytic process realized over LaSBA-15(pH) samples. The acid sites presence in these samples, associated to their large average pore sizes and high surface areas, have allowed them, especially the La75SBA-15(pH), to present deoxygenating activity in the buriti oil thermal catalytic cracking, providing an oxygenates content reduction, particularly carboxylic acids, in the GD. Furthermore, the GD comes from the second liquid fraction obtained in the buriti oil thermal catalytic cracking over this latest solid sample has shown hydrocarbons composition and physic-chemical properties similar to that mineral diesel, beyond sulfur content low / Com o objetivo de obter um biocombust?vel semelhante ao diesel mineral, materiais nano-estruturados do tipo SBA-15 com lant?nio incorporado, LaSBA-15(pH), com raz?es molares Si/La = 75, 50 e 25, foram sintetizados em dois est?gios, com ajuste do pH do gel de s?ntese a 6, e utilizados como s?lidos catal?ticos no craqueamento termocatal?tico de ?leo de buriti. As amostras s?lidas foram caracterizadas por fluoresc?ncia de raios-X (FRX), difra??o de raios-X (DRX), an?lise termogravim?trica (TG/DTG), espectroscopia na regi?o do infravermelho (FTIR), adsor??o-dessor??o de nitrog?nio e desidrata??o de etanol, para identifica??o dos s?tios ativos. Os resultados destas caracteriza??es indicaram que o m?todo de s?ntese empregado proporcionou a obten??o de materiais mesoestruturados altamente ordenados com grande di?metro m?dio de poros e elevada ?rea superficial, al?m de sugerir que o lant?nio foi incorporado na SBA-15 tanto no interior das paredes, quanto dentro dos mesoporos. A desidrata??o catal?tica de etanol sobre os s?lidos LaSBA-15(pH) mostrou que eles apresentam s?tios ?cidos e b?sicos de Lewis, indicativo da presen?a de ?xido de lant?nio nestes, especialmente na amostra La75SBA-15(pH), que apresentou a maior seletividade para etileno. Os craqueamentos t?rmico e termocatal?ticos do ?leo de buriti, realizados da temperatura ambiente a 450 ?C em um sistema de destila??o simples, possibilitaram a obten??o de duas fra??es l?quidas, compostas por duas fases, uma aquosa e outra org?nica, l?quido org?nico (LO). O LO obtido a partir das primeiras fra??es apresentou ?ndice de acidez muito elevado, at? mesmo nos processos termocatal?ticos. Por outro lado, o LO oriundo das segundas fra??es, denominado de diesel verde (DV), apresentou baixo ?ndice de acidez, particularmente aquele obtido nos processos realizados sobre as amostras LaSBA-15(pH). Os s?tios ?cidos presentes nestas amostras, associados aos seus grandes di?metros m?dios de poros e ?s elevadas ?reas superficiais, permitiram que elas, especialmente a La75SBA-15(pH), apresentassem atividade desoxigenante no craqueamento temocatal?tico do ?leo de buriti, ocasionando uma diminui??o da concentra??o de oxigenados no DV, particularmente ?cidos carbox?licos. Al?m disso, o DV obtido sobre esta ?ltima amostra s?lida apresentou composi??o de hidrocarbonetos e propriedades f?sico-qu?micas semelhantes ?s do diesel mineral, al?m de um baixo teor de enxofre

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