Thesis (MScEng (Industrial Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The world is facing an energy crisis with worldwide energy consumption rising at an alarming rate. The effects that fossil fuels have on the environment are also causing concern. For these two reasons the world is determined to find ‘cleaner’, renewable and sustainable energy sources. The Cape Winelands District Munisipality (CWDM) area has been identified as the study area for a bioenergy project. The CWDM project aims to determine the possibility of producing bioenergy from lignocellulosic biomass, and transporting it as economically as possible to a number of electricity plants within the study area. From the CWDM project a number of research topics were identified. The aim of this thesis is to determine the best location for one or more processing plants that will maximise the potential profit through the entire system. This is achieved by minimising the overall life cycle cost of the project. It takes into account costs from establishing and maintaining the crops, harvesting, transportation, conversion and generation; with a strong focus on the transport costs. In conjunction with a Geographical Information Systems (GIS) specialist and taking into account various factors such as electricity demand, heat sales and substation locations, 14 possible plant locations were identified. The possible supply points for each of the 14 plant locations were then analysed by GIS again to yield data in terms of elevation, road distances and slope. The transport costs were calculated using the Vehicle Cost Schedule (VCS) from the Road Freight Association (RFA) and fuel consumption calculations. It takes into account slope, laden and unladen transport and considers different transport commodities. These calculations together with the other associated costs of the life cycle are then combined with the results of the GIS into an EXCEL file. From this a transportation optimisation model is developed and the equivalent yearly life cycle cost of each of the 14 demand points are minimised by means of LINGO software. Initially runs were done for 2.5 MW capacity plants. From the high profit areas identified here, a single area was chosen and further runs were done on it. These runs were performed to determine the effect of different plant capacities on the life cycle costs, as well as how it affects the farm gate price that can be paid to the farmer. It also determined the effect of farmer participation at different plant capacities. The results indicate that it is currently possible to pay a farmer between R 300.00 and R 358.00 for a ton of biomass. It also revealed that with higher participation from farmers in the CWDM project, lower costs and higher farm gate prices will result, since the transport costs will be lower. Although all the costs within the life cycle are variable over time, the transport cost is the only cost that varies spatially and this will have a major effect on the overall system cost. The thesis found that generating electricity from woody biomass is feasible for all areas that were considered as well as for all variations considered during the sensitivity analysis. For the recommended plant size of 5 MW the transport of logs will be optimum. / AFRIKAANSE OPSOMMING: Die tempo waarteen energieverbruik wêreldwyd styg is ʼn rede tot kommer. Die nadelige effek wat fossiel brandstowwe op die omgewing het, is ook ʼn probleem. Hierdie twee redes is hoofsaaklik wat die wêreld dryf om ‘skoner’ hernieubare en volhoubare energie bronne te vind. Die Kaapse Wynland Distrik Munisipaliteit (KWDM) area is identifiseer as ʼn studie area vir ʼn bio-energie projek. Die doel van die KWDM projek is om die vervaardiging van bio-energie vanaf plantasies, die vervoer van hierdie bome sowel as die prosessering koste by die fabriek te bepaal en te evalueer. Vanuit die KWDM projek het `n aantal tesisse ontwikkel waarvan hierdie een is. Die doel van hierdie tesis is om die beste posisie vir een of meer prosesserings fabrieke te bepaal wat die potensiële wins van die KWDM projek sal maksimeer. Dit is ook gemik daarop om die ekwivalente jaarlikse oorhoofse lewenssiklus koste van die projek te minimeer. Dit neem die vestiging en onderhoud van gewasse, oeskostes, vervoerkostes en proseskostes in ag, met ʼn spesifiek fokus op die vervoerkoste. In samewerking met `ʼn “Geographical Information Systems” (GIS) spesialis en deur verskeie faktore, soos elektrisiteitsverbruik, inkomste vanaf hitte verkope en substasie posisies, in ag te neem is 14 moontlike fabriek posisies identifiseer. Verder is die moontlike voorsienings areas van elk van die 14 fabriek posisies weer deur GIS analiseer om resultate in terme van hoogte bo seespieël, padafstand en helling te verkry. Die vervoerkostes is verkry vanaf die “Vehicle Cost Schedule” (VCS) van die “Road Freight Association” (RFA), asook berekeninge wat die brandstof verbruik in ag neem. Hierdie kostes sluit in die effek van gradiënt, gelaaide en ongelaaide vervoer sowel as verskillende vervoer produkte. Hierdie berekeninge sowel as die ander kostes in die siklus en die resultate van GIS is kombineer in ʼn EXCEL leer. Hierdie data word dan gebruik om ʼn LINGO model te ontwikkel en die oorhoofse lewenssiklus koste van elk van die 14 fabriek posisies te minimeer. Optimering is gedoen vir 2.5 MW kapasiteit fabrieke. Uit die beste areas is een area identifiseer en verdere lopies is daarop gedoen. Die doel van hierdie lopies is om die effek van verskillende fabriekskapasiteit op die lewensiklus koste te bepaal, asook die effek daarvan op die prys wat aan die boer betaal word vir hout. Hierdie lopies is ook gebruik om die effek van boer deelname te bepaal. Die resultaat dui aan dat dit tans moontlik is om ʼn boer tussen R 300.00 en R 358.00 te betaal vir ʼn ton biomassa. Dit het ook gewys dat hoe meer boere deelneem aan hierdie projek hoe laer is die oorhoofse lewensiklus koste en hoe hoër is die prys wat betaal kan word vir hout aangesien die vervoerkoste laer sal wees. Alhoewel al die lewensiklus kostes veranderlik is oor tyd, is dit net die vervoerkoste wat ʼn ruimtelike komponent ook het en dit sal ʼn groot effek op die oorhoofse lewenssiklus koste hê. Die tesis bevind dat dit lewensvatbaar is vir alle areas in die studie om elektrisiteit op te wek vanaf hout biomassa, selfs al word die uiterse variasie in die sensitiwiteitsanalise gebruik. Vir die aanbeveling van ʼn 5 MW fabriek sal die goedkoopste vervoer opsie boomstompe wees.

The research reported here explored, a "new" approach to biomass energy conversion for small-scale process heat-applications. The conversion process uses close-coupled catalytic. combustion to burn combustibles in effluent generated by primary combustion or gasification of biomass fuels. Computer control of primary and secondary air flow rates allow control of the devices output power while maintaining fuel-lean or stoichiometric conditions in the effluent entering the catalytic combustion zone. The intent of the secondary combustion system is to ensure "clean" exhaust (i.e., promote complete combustion). A small-scale combustor/gasifier was built and instrumented. Characteristics of combustion were studied for three biomass fuels so that primary and secondary air flow control strategies could be devised. A bang-bang type controller was devised for primary air flow control. Secondary air as controlled based on feedback signals from an inexpensive automobile exhaust gas oxygen sensor. The control strategies and catalytic combustion were implemented on prototype combustor/gasifier and the device was tested with good results. Power turn down ratios of 4 to 1 and 3 to 1 were achieved. The zitconia-type automobile exhaust gas oxygen sensors adapted well to the combustion environment of biomass fuel, at least for short periods (long term durability tests were not conducted). The secondary air control system was able to maintain fuel-lean flows for the most part and, the secondary combustion system provided reductions of approximately three fourths in carbon monoxide emissions. / Master of Science

This thesis develops quantitative methods for evaluation and design of large-scale biofuel production systems with a particular focus on bioreactor-based fuel systems. In Chapter 2, a lifecycle assessment (LCA) method is integrated with chemical process modeling to select from different process designs the one that maximizes the energy efficiency and minimizes the environmental impact of a production system. An algae-based ethanol production technology, which is in the process of commercialization, is used as a case study. Motivated by this case study, Chapter 3 studies the selection of process designs and production capacity of highly distributed bioreactor-based fuel system from an economic perspective. Nonlinear optimization models based on net present value maximization are developed that aim at selecting the optimal capacities of production equipment for both integrated and distributed-centralized process designs on symmetric production layouts. Global sensitivity analysis based on Monte Carlo estimates is performed to show the impact of different parameters on the optimal capacity decision and the corresponding net present value. Conditional Value at Risk optimization is used to compare the optimal capacity for a risk-neutral planner versus a risk-averse decision maker. Chapter 4 studies mobile distributed processing in biofuel industry as vehicle routing problem and production equipment location with an underlying pipeline network as facility location problem with a focus on general production costs. Formulations and algorithms are developed to explore how fixed cost and concavity in the production cost increases the theoretical complexity of these problems.

Orientador: Gilberto De Martino Jannuzzi / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-06T16:21:54Z (GMT). No. of bitstreams: 1 Sanga_GodfreyAlois_M.pdf: 971523 bytes, checksum: 2bed5a0581e8c38cc4126dcaca4366bb (MD5) Previous issue date: 2004 / Resumo: O objetivo deste trabalho é verificar quantitativamente os impactos de melhoria de eficiência e de substituição de combustíveis para cocção na cidade de Dar es Salaam, na Tanzânia. Neste trabalho foi realizada uma pesquisa, enfocando os países em desenvolvimento, sobre energia para cocção e as características que definem a energia limpa, baseado nos recomendados padrões de eficiência e de emissão de gases poluentes e substâncias particuladas. Discute-se, também os mecanismos de promoção e popularização das tecnologias eficientes e dos combustíveis limpos. E seguidamente, o trabalho apresenta uma análise comparativa entre a melhoria de eficiência e a substituição de combustíveis em relação à demanda de energia para cocção, poluição do ar em ambientes fechados, emissão de gases de efeito estufa e custos. Espera-se que este trabalho seja útil na formação de políticas para melhorar a oferta de energia para cocção em Dar es Salaam como também para reduzir o desmatamento, poluição do ar em ambientes fechados e a emissão de gases de efeito estufa provenientes de uso de combustíveis tradicionais na Tanzânia / Abstract: The objective of this study is to verify quantitatively the impacts of energy efficiency improvements and cooking fuels substitution in Dar es Salaam, Tanzania. The analysis focuses on developing countries and entails infonnation on access to cooking fuels, technologies and characteristics which defme a clean cooking 'energy based on the recommended efficiency and emissions standards. It also analyses various promotion and dissemination mechanisms for different energy efficient technologies and clean cooking fuels. Finally, the study presents a comparative analysis of energy efficiency improvement and fuel substitution in terms of cooking energy demand, indoor air pollution, emission of green house gases and costs. It is hoped that this work will be useful in policy fonnulation to improve energy supply in Dar es Salaam as well as in reducing tree depletion, indoor air pollution and emissions of greenhouse gases from the use of charcoal in Tanzania / Mestrado / Mestre em Planejamento de Sistemas Energéticos

New federal legislation proposes to reduce greenhouse gas (GHG) emissions associated with biofuel production. To comply, existing corn ethanol plants will have to invest in new more carbon efficient production technology such as dry fractionation. However, this will be challenging for the industry given the present financial environment of surplus production, recent profit declines, numerous bankruptcies, and lender imposed covenants. This study examines a dry-mill ethanol firm's ability to invest in dry fractionation technology in the face of declining profitability and stringent lender cash flow repayment constraints. Firm level risk aversion also is considered when determining a firm's willingness to invest in dry fractionation technology. A Monte Carlo simulation model is constructed to estimate firm profits, cash flows, and changes in equity following new investment in fractionation to determine an optimal investment strategy. The addition of a lender-imposed sweep, whereby a percentage of free cash flow is used to pay off extra debt in high profit years, reduces the firm's ability to build equity and increases bankruptcy risk under investment. However, the sweep increases long-run equity because total financing costs are reduced with accelerated debt repayment. This thesis shows that while ethanol firm profits are uncertain, the lender's imposition of a sweep combined with increased profit from dry fractionation technology help the firm increase long-run financial resiliency.

Call number: LD2668 .T4 1984 G666 / Master of Science

Submitted in fulfilment of the requirements of the Degree of Master of Technology: Biotechnology, Durban University of Technology, 2011. / Due to greenhouse gas emissions from fossil fuel usage, the impending threat of global climate change has increased. The need for an alternative energy feedstock that is not in direct competition to food production has drawn the focus to microalgae. Research suggests that future advances in microalgal mass culture will require closed systems as most microalgal species of interest thrive in highly selective environments. A high lipid producing microalga, identified as Chlorella vulgaris was isolated from a freshwater pond. To appraise the biofuel potential of the isolated strain, the growth kinetics, pyroletic characteristics and photosynthetic efficiency of the Chlorella sp was evaluated in vitro. The optimised preliminary conditions for higher biomass yield of the selected strain were at 4% CO2, 0.5 g l-1 NaNO3 and 0.04 g l-1 PO4, respectively. Pulse amplitude modulation results indicated that C. vulgaris could withstand a light intensity ranging from 150-350 μmol photons m-2s-1. The pyrolitic studies under inert atmosphere at different heating rates of 15, 30, 40 and 50 ºC min-1 from ambient temperature to 800 oC showed that the overall final weight loss recorded for the four different heating rates was in the range of 78.9 to 81%. A tubular photobioreactor was then designed and utilised for biomass and lipid optimisation. The suspension of microalgae was circulated by a pump and propelled to give a sufficiently turbulent flow periodically through the illuminated part and the dark part of the photobioreactor. Microalgal density was determined daily using a Spectrophotometer. Spectrophotometric determinations of biomass were periodically verified by dry cell weight measurements. Results suggest that the optimal NaNO3 concentration for cell growth in the reactor was around 7.5 g l-1, yielding maximum biomass of 2.09 g l-1 on day 16. This was a significant 2.2 fold increase in biomass (p < 0.005) when compared to results achieved at the lowest NaNO3 cycle (of 3.8 g l-1), which yielded a biomass value of 0.95 g l-1 at an OD of 1.178. Lipid accumulation experiments revealed that the microalga did not accumulate significant amounts of lipids when NaNO3 concentrations in the reactor were beyond 1.5 g l-1 (p > 0.005). The largest lipid fraction occurred when the NaNO3 concentration in the medium was 0.5 g l-1. Results suggest that the optimal trade-off between maximising biomass and lipid content occurs at 0.9 g l-1 NaNO3 among the tested conditions within the photobioreactor. Gas chromatograms showed that even though a greater number of known lipids were produced in Run 8, the total lipid percentage was much lower when compared to Runs 9-13. For maximal biomass and lipid from C. vulgaris, it is therefore crucial to optimise nutritional parameters such as NaNO3. However, suitable growth conditions for C. vulgaris in a tubular photobioreactor calls for innovative technological breakthroughs and therefore work is ongoing globally to address this.

Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: In recent times, governments around the world have placed increasing focus on cleaner technologies and sustainable methods of power generation in an attempt to move away from fossil fuel derived power, which is deemed unsustainable and unfriendly to the environment. This trend has also been supported by the South African government, with clear intentions to diversify the country’s power generation by including, among others, biomass as a renewable resource for electricity generation. Woody biomass and associated forestry residues in particular, could potentially be used as such a renewable resource when considering the large amount of fast growing hardwood species cultivated in South Africa. Approximately 6.3 million ton of Eucalyptus grandis is sold annually for pulp production while a further 7 million ton of Eucalyptus species are sold as round wood. With these tree species reaching commercial maturity within 7 – 9 years in the South African climate, there is real potential in harnessing woody biomass as a renewable energy source. In this study, pyrolysis was investigated as a method to condense and upgrade E.grandis into energy and chemical rich products. The pyrolysis of E.grandis is the study of the thermal degradation of the biomass, in the absence of oxygen, to produce char and bio-oil. The thermal degradation behaviour of E.grandis was studied using thermo-gravimetric analysis (TGA) at the Karlsruhe Institute of Technology (KIT) in Germany and subsequently used to determine the isoconversional kinetic constants for E.grandis and its main lignocellulosic components. Slow, Vacuum and Fast Pyrolysis were investigated and optimised to maximise product yields and to identify the key process variables affecting product quality. The Fast Pyrolysis of E.grandis was investigated and compared on bench (KIT0.1 kg/h), laboratory (SU1 kg/h) and pilot plant scale (KIT10 kg/h), using Fast Pyrolysis reactors at Stellenbosch University (SU) in South Africa and at KIT in Germany. The Slow and Vacuum Pyrolysis of E.grandis was investigated and compared using a packed bed reactor at Stellenbosch University. The TGA revealed that biomass particle size had a negligible effect on the thermal degradation behaviour of E.grandis at a heating rate set point of 50 °C/min. It was also shown that increasing the furnace heating rates shifted the thermo-gravimetric (TG) and differential thermo-gravimetric (DTG) curves towards higher temperatures while also increasing the maximum rate of volatilisation. Lignin resulted in the largest specific char yield and also reacted across the widest temperature range of all the samples investigated. The average activation energies found for the samples investigated were 177.8, 141.0, 106.2 and 170.4 kJ/mol for holocellulose, alpha-cellulose, Klason lignin and raw E.grandis, respectively. Bio-oil yield was optimised at 76 wt. % (daf) for the SU1 kg/h Fast Pyrolysis plant using an average biomass particle size of 570 μm and a reactor temperature of 470 °C. Differences in the respective condensation chains of the various Fast Pyrolysis reactor configurations investigated resulted in higher gas and char yields for the KIT reactor configurations compared to the SU1 kg/h Fast Pyrolysis plant. Differences in the vapour residence time between Slow (>400 s) and Vacuum Pyrolysis (< 2 s) resulted in a higher liquid and lower char yield for Vacuum Pyrolysis. Local liquid yield maxima of 41.1 and 64.4 wt. % daf were found for Slow and Vacuum Pyrolysis, respectively (achieved at a reactor temperature of 450 °C and a heating rate of 17 °C/min). Even though char yields were favoured at low reactor temperatures (269 – 300 °C), the higher heating values of the char were favoured at high reactor temperatures (29 – 34 MJ/kg for 375 – 481 °C). Reactor temperature had the most significant effects on product yield and quality for the respective Slow and Vacuum Pyrolysis experimental runs. The bio-oils yielded for SP and VP were found to be rich in furfural and acetic acid. / AFRIKAANSE OPSOMMING: Regerings regoor die wêreld het in die afgelope tyd toenemende fokus geplaas op skoner tegnologie en volhoubare metodes van kragopwekking in 'n poging om weg te beweeg van fossielbrandstof gebasseerde energie, wat geag word as nie volhoubaar nie en skadelik vir die omgewing. Hierdie tendens is ook ondersteun deur die Suid-Afrikaanse regering, met 'n duidelike bedoeling om die land se kragopwekking te diversifiseer deur, onder andere, biomassa as 'n hernubare bron vir die opwekking van elektrisiteit te gebruik. Houtagtige biomassa en verwante bosbou afval in die besonder, kan potensieel gebruik word as so 'n hernubare hulpbron, veral aangesien ‘n groot aantal vinnig groeiende hardehout spesies tans in Suid-Afrika verbou word. Ongeveer 6,3 miljoen ton Eucalyptus grandis word jaarliks verkoop vir pulp produksie, terwyl 'n verdere 7 miljoen ton van Eucalyptus spesies verkoop word as paal hout. Met hierdie boom spesies wat kommersiële volwassenheid bereik binne 7 - 9 jaar in die Suid-Afrikaanse klimaat, is daar werklike potensiaal vir die benutting van houtagtige biomassa as 'n hernubare energiebron. In hierdie studie is pirolise ondersoek as 'n metode om E.grandis te kondenseer en op te gradeer na energie en chemikalie ryke produkte. Die pirolise van E.grandis is die proses van termiese afbreking van die biomassa, in die afwesigheid van suurstof, om houtskool en bio-olie te produseer. Die termiese afbrekingsgedrag van E.grandis is bestudeer deur gebruik te maak van termo-gravimetriese analise (TGA) by die Karlsruhe Instituut van Tegnologie in Duitsland en daarna gebruik om die kinetiese konstantes vir die iso-omskakeling van E.grandis en sy hoof komponente te bepaal. Stadige, Vakuum en Snel pirolise is ondersoek en geoptimiseer om produk opbrengste te maksimeer en die sleutel proses veranderlikes wat die kwaliteit van die produk beïnvloed te identifiseer. Die Snel Pirolise van E.grandis is ondersoek en vergelyk op bank- (KIT0.1 kg / h), laboratorium- (SU1 kg / h) en proefaanlegskaal (KIT10 kg / h) deur gebruik te maak van Snel pirolise reaktore by die Universiteit van Stellenbosch (US) in Suid-Afrika en die Karlsruhe Instituut van Tegnologie (KIT) in Duitsland. Die Stadige en Vakuum Pirolise van E.grandis is ondersoek en vergelyk met behulp van 'n gepakte bed reaktor aan die Universiteit van Stellenbosch. Die TGA studie het openbaar dat biomassa deeltjiegrootte 'n onbeduidende uitwerking op die termiese afbrekingsgedrag van E.grandis het by 'n verhittings tempo van 50 ° C / min. Dit is ook bewys dat die verhoging van die oond verwarming tempo die termo-gravimetriese (TG) en differensiële termo-gravimetriese (DTG) kurwes na hoër temperature verskuif, terwyl dit ook die maksimum tempo van vervlugtiging laat toeneem het. Lignien het gelei tot die grootste spesifieke houtskool opbrengs en het ook oor die wydste temperatuur interval gereageer van al die monsters wat ondersoek is. Die gemiddelde aktiveringsenergieë vir die monsters wat ondersoek is, was 177,8, 141,0, 106,2 en 170,4 kJ / mol, onderskeidelik vir holosellulose, alpha-sellulose, Klason lignien en rou E.grandis. Bio-olie opbrengs is geoptimeer teen 76 wt. % (DAF) vir die SU1 kg / h Snel Pirolise aanleg met behulp van 'n gemiddelde biomassa deeltjiegrootte van 570 μm en 'n reaktor temperatuur van 470 ° C. Verskille in die onderskeie kondensasie kettings van die verskillende Snel Pirolise aanlegte wat ondersoek is, het gelei tot hoër gas- en houtskool opbrengste vir die KIT reaktor konfigurasies in vergelyking met die SU1kg/h FP plant. Verskille in die damp retensie tyd tussen Stadige (> 400 s) en Vakuum pirolise (<2 s) het gelei tot 'n hoër vloeistof en laer houtskool opbrengs vir Vakuum Pirolise. Plaaslike vloeistof opbrengs maksima van 41,1 en 64,4 wt. % (daf) is gevind vir Stadig en Vakuum pirolise onderskeidelik, bereik by 'n reaktor temperatuur van 450 ° C en 'n verhittingstempo van 17 ° C / min. Selfs al is houtskool opbrengste bevoordeel by lae reaktor temperature (269 - 300 ° C), is die hoër warmte waardes van die houtskool bevoordeel deur hoë reaktor temperature (29 - 34 MJ / kg vir 375 - 481 ° C). Reaktor temperatuur het die mees beduidende effek op die produk opbrengs en kwaliteit vir die onderskeie Stadige Pirolise en Vakuum Pirolise eksperimentele lopies gehad. Die bio-olies geproduseer tydens Stadige en Vakuum Pirolise was ryk aan furfuraal en asynsuur.

Reducing anthropogenic GHG emissions globally is a key driver for the development of renewable energy sources. A key route towards achieving this is to replace fossil-based fuels with renewable and low carbon energy technologies such as biofuels from energy crops. Cereals and oil-seed crops such as corn, wheat, and soybean are the main feedstocks primarily used for biofuels production and the key characteristics of these crops are high biomass and energy yield per ha. However, there are concerns about the availability and sustainability of these crops for biofuels production in the face of a changing climate since crop productivity is inherently sensitive to climate. Therefore, an understanding of the impacts of climate change on energy crops production as feedstocks for biofuels production and their potential for life cycle GHG emissions reductions is crucial for making decisions on future biofuels production. This thesis examined potential climate change impacts on the productivity of two major biofuel crops: corn (Zea mays L.) and soybean (Glycine max) in Gainesville, USA and one major biofuel crop: wheat (Triticum spp.) in Rothamsted, UK. The overall objective was to calculate the potential impacts of combined changes in climate variables: surface air temperature (T), precipitation (P), and atmospheric concentration of CO2 ([CO2]) on life cycle GHG emissions savings of biofuels from corn, soybean, and wheat. The methodology was underpinned by life cycle thinking. Life cycle assessment (LCA) models linked to cropping system models (CSM) were used in the analysis. In assessing the impact of climate change on corn, wheat, and soybean crops yields, two applications of the CERES (Crop-Environment Resource Synthesis) model: CERES-Wheat (for wheat) and CERES-Maize (for corn), and CROPGRO (Crop Growth) model application: CROPGRO-Soybean of the Decision Support System for Agrotechnology Transfer (DSSAT-CSM) v4.0.2.0 model were used using observed weather data from the baseline (1981-1990) period for each study site. These models describe, based on daily data, the basic biophysical processes taking place at the soil-plant-atmosphere interface as a response to the variability of different processes such as: photosynthesis, specific phenological phases, evapotranspiration, and water dynamics in soil. Compared with the baseline, T was projected to increase by +1.5, +2, +2.5, +3, +3.5, +4, +4.5, and +5 oC, P was projected to change by ±5, ±10, ±15, and ±20%, and [CO2] was projected to increase by +70, +140, +210, +280, and + 350 ppm for Gainesville, USA. For Rothamsted, UK, T was projected to increase by +0.5, +1.5, +2.5, +3.5, and +4.5 oC, P was projected to change by ±10, and ±20%, and [CO2] was projected to increase by +70, +210, and + 350 ppm. Simulated yields output (grain/seeds and biomass) from the CSM models were used as inputs into the LCA models. Potential life cycle GHG emissions savings were calculated for corn-based biofuels: corn bioethanol (CBE), corn integrated biomethanol (CIBM), and corn integrated bioelectricity (CIBE); soybean-based biofuels: soybean biodiesel (SBD), soybean integrated biomethanol (SIBM), and soybean integrated bioelectricity (SIBE); wheat-based biofuels: wheat bioethanol (WBE), wheat integrated biomethanol (WIBM), and wheat integrated bioelectricity (WIBE). Results indicated that under the baseline (1981-1990) scenario, production and use of CBE, CIBM, CIBE, SBD, SIBM, SIBE, WBE, WIBM, and WIBE could save -4743.32 kg CO2-equiv. ha-1, -8573.31 kg CO2-equiv. ha-1, and -10996.7 kg CO2-equiv. ha-1, -2655.41 kg CO2-equiv. ha-1, -3441.1 kg CO2-equiv. ha-1, and -1350.04 kg CO2-equiv ha-1, -2776.1 kg CO2-equiv. ha-1, -500.87 kg CO2-equiv. ha-1 and -4648.93 kg CO2-equiv. ha-1 respectively, of the total life cycle GHG emissions of CO2, CH4, and N2O for the production and utilization of an energetically equivalent amount of fossil-based fuel counterpart, which they displaced. However, model predictions of future life cycle GHG emissions savings for both crops showed that the responses of corn, soybean, and wheat to simultaneous changes in T, P, and [CO2] were different under different climate change scenarios. In the future period life cycle GHG emissions savings of corn-based biofuels was predicted to decline in all cases ranging from -4.2% to -46.1%, -2.6% to -37.7%, and -1.6% to -33.4% for CBE, CIBM, and CIBE, respectively compared with the baseline (1981-1990) period. In contrast, model predictions showed that life cycle GHG emissions savings of wheat-based biofuels would increase under all climate change scenarios ranging from +2.5% to +33.5%, +0.1% to +37.8%, and +1.0% to +34.4% for WBE, WIBM, and WIBE, respectively. On the other hand, the life cycle GHG emissions savings of soybean-based biofuels was predicted to increase by +0.22% to +27%, +0.1% to 28%, and +0.1% to +31.6% for SBD, SIBM, and SIBE, respectively under some climate change scenarios (e.g., [CO2] = 680; P = +20%; and T = +1.5 oC scenario) and also decline by -0.7% to -60.8%, -0.1% to -44.6%, and -0.1% to -82.6% for SBD, SIBM, and SIBE, respectively under some climate change scenarios (e.g., [CO2] = 400; P = -20%; and T = +5 oC scenario). These results revealed that the potential impacts of climate change on energy crops productivity and net life cycle GHG emissions savings could be very large and diverse, and that the anticipated life cycle GHG emissions reductions of biofuels would not be the same in the future.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Development of analytical methods to characterise biodiesel has become central to the overall success of the marketing of biodiesel fuel. In this regard, different bodies including the American Society for Testing and Materials (ASTM) and the European normalization (EN) have come up with various methods to determine important biodiesel parameters such as total glycerol, methanol and the fatty acid methyl esters (FAMEs), etc. Various studies have been conducted on the parameters mentioned above using a variety of instrumentation and sample preparations. The best methods reported are those that have been adopted by both the ASTM and EN standards. The purpose of this study was to develop alternative analytical methods to both the recommended ASTM and EN methods and, in some cases, to make modifications to both standards (ASTM D 6571 and EN 14214) and methods to determine total and bound glycerol, the ester content and also methanol content in biodiesel. Moreover, water washing after transesterification and the effect this practice has on biodiesel cold flow properties such as kinematic viscosity, cloud and pour point and density were evaluated. The possibility of using the iodine value to predict the feedstock source of an unknown biodiesel was also investigated. Six different vegetable oil samples were transesterified with methanol and used for this study. The six samples used were palm, crown, sunflower, waste vegetable oil (wvo), peanut and rapeseed biodiesel. Quantitative results indicated that the use of programmable temperature volatilisation (PTV) for total glycerol did not produce the required repeatability of between 1-4% relative standard deviation(RSD) for total glycerol analyses in biodiesel with precision of 25%, 86%, 25% and 56% for free glycerol (FG), monoglycerides (MG), diglycerides (DG), and triglycerides (TG) respectively. The standard requires a relative standard of between 1-4% As an alternative to the method using gas chromatography, normal phase high performance chromatography (HPLC) with binary gradient elution was used to determine the bound glycerol content. This method proved accurate and repeatable with RSD % of 0.33, 1.12, and 1.2 for TG, DG and MG respectively. Following the EN14103 protocol (European standard ester determination), the Zebron ZBWAX column which is comparable to the specification recommended by EN14103 but afforded the determination of ester content from the esters of myristic acid (C14:0) to behenic acid (C22:0) with reproducibility with RSD % of 6.81, 1.91, 7.27, 0.64, 1.18, 1.55, 6.03, 1.96, and 5.21 for methyl esters of myristic, palmitic, stearic, oleic, linoleic, linolenic, arachidoic, gadoleic and behenic acid respectively. Solid phase micro extraction (SPME) using GC-MS was developed as an alternative to both the EN14110 and ASTM D93 protocols for determining the methanol content in biodiesel. For this method, polyethylene glycol fibre (PEG) was used together with a deuterated methanol internal standard and a DB-FFAP (60m×0.25um×0.25um) column. Less volume of sample was required as compared to the EN14214 method. This method was found to be sensitive, accurate and repeatable with a RSD % of 4.82. The Iodine number of biodiesel decrease compared to their corresponding feed stock and therefore predicting the feed stock of an unknown biodiesel was going to be difficult .Results from this study indicated that it is not possible to predict the feed stock source of an unknown biodiesel from its iodine value. The effect of water washing after phase separation on biodiesel cold flow properties such as kinematic viscosity, density, cloud and pour point depended on the type of biodiesel produced. We observed that water washing after transesterification caused an increase in all the cold flow properties of sunflower biodiesel, whereas only the densities and kinematic viscosities increased in the case of palm and waste vegetable oil biodiesel. The cloud and pour point of the latter two diesel samples remained unchanged after water washing. Thus, the effect of water washing on biodiesel cold flow depended on the type of biodiesel. Blending a highly saturated biodiesel (fewer numbers of double bonds) with a less saturated biodiesel (higher number of double bonds) resulted in an improvement of both the pour and cloud points of the resultant biodiesel blend. / AFRIKAANSE OPSOMMING: Die ontwikkeling van analitiese metodes om biodiesel te karakteriseer word tans as ‘n kernmaatstaf gesien om biodiesel suksesvol te bemark. Hiervoor het verskeie liggame wat die Amerikaanse Vereniging vir Toetsing van Materiale (AVTM) en die Europese Normalisering (EN) insluit met verskeie standaard analitiese metodes vorendag gekom om belangrike biodiesel parameters soos bv. totale gliserol, metanol en vetsuur metielesters te meet. Om hierdie parameters te bepaal is van ‘n wye verskeidenheid toetse met verskillende instrumente en monsterbereidings gebruik gemaak. Die beste metodes is deur beide die AVTM en EN aanvaar. Die doel van hierdie studie was om metodes te ontwikkel wat as alternatiewe kan dien tot die wat deur die AVTM en EN voorsgeskryf is. In sommige gevalle is aanpassings tot beide die standaarde (AVTM en EN) en metodes aangebring om die totale en gebonde gliserol-, esteren metanolinhoud te bepaal. Verder is die effek van ‘n water wasstap na transesterifikasie op biodiesel se kouevloei eienskappe gevalueer wat eienskappe soos kinematiese viskositeit, vertroebelingspunt, gietingspunt en digtheid insluit. Die moontlike gebruik van die Jodiumpunt om die bron van die voerstof van ‘n onbekende diesel te bepaal is ook ondersoek. In hierdie studie is ses verskillende oliemonsters van plantaardige oorsprong gebruik wat d.m.v. metanol getransesterifiseer is. Hierdie monsters het palm-, kroon-, sonneblom-, afvalplant-, grondboontjie- en raapsaadolie ingelsuit. Tydens die studie is programmeerbare temperatuur vervlugtiging (PTV) vergelyk met inkolom inspuiting soos deur AVTM D6584/EN14214 vir totale gliserol analise voorgeskryf. Kwantitatiewe resultate het getoon dat die PTV metode nie die verlangde akkuraatheid van ‘n relatiewe standaardafwyking (RS) van 1-4% vir beide vrye en gebonde gliserol kon handhaaf nie. Die akkuraatheid was in die omgewing van 25%, 86%, 25% en 56% vir vrye gliserol (VG), monogliseriede (MG), digliseriede (DG) en trigliseriede (TG), onderskeidelik. Normale fase hoë werkverrigting vloeistofchromatografie met ‘n binêre elueeringsgradiënt is as alternatief tot gaschromatografie (GC) ondersoek om die gebonde gliserolinhoud te bepaal. Al was die GC metode meer sensitief, het die vloeistofchromatografie metode ‘n hoë graad van akuraatheid en herhaalbaarheid getoon met RS% waardes van 0.33, 1.12 en 1.2 wat vir TG, DG en MG, onderskeidelik, verkry is. ‘n Zebron ZB-WAX kolom is vir die EN14103 protokol gebruik. Behalwe vir ‘n groter lengte kon hierdie kolom met spesifikasies soos deur EN14103 voorgeskryf vergelyk word. Met die gebruik van hierdie kolom kon die esterinhoud van miristiensuur (C14:0) tot behensuur (C14:0) bepaal word. ‘n Hoë graad van herhaalbaarheid met RS% waardes van 6.81, 1.91, 7.27, 0.64, 1.18, 1.55, 6.03, 1.96 en 5.21 vir die metielesters van miristien-, palmitien-, stearien-, oleïn-, linoleïn-, linoleen-, aragidoon-, gadoleïen- en behensuur is onderskeidelik verkry. Om die metanolinhoud van die biodiesel te bepaal is soliede fase mikroekstraksie (SFME) m.b.v. gaschromatografie-massaspektrometrie (GC-MS) as alternatiewe tot EN14110 en AVTM D93 ontwikkel. In hierdie metode is daar van poliëtileenglikolvesels (PEG) en gedeutereerde metanol saam met ‘n DB-FFAP kolom (60 mm x 0.25 mm x 0.25 mm) gebruik gemaak. Hierdie metode het ‘n kleiner monstervolume as die EN14214 metode benodig en was sensitief, akkuraat en hehaalbaar wat tot ‘n RS% waarde van 4.82 gelei het. Op grond van die Jodiumwaarde van biodiesel en hul ooreenstemmende voerstowwe het hierdie studie bevind dat die Jodiumwaarde nie gebruik kan word om die voerstof van ‘n onbekende diesel kan voorspel nie. Die effek van ‘n water wasstap na faseskeiding op verskeie kouevloei eienskappe soos kinematiese viskositeit, vertroebelingspunt, gietingspunt en digtheid het van die tipe diesel afgehang. Dit is bevind dat ‘n water wasstap na transesterifikasie ‘n toename in al die kouevloeieienskappe van sonneblomdiesel tot gevolg gehad het. In teenstelling hiermee het slegs die kinematiese viskositeit en digtheid van palm- en afvalplantdiesel vermeerder terwyl hul vertroebelings- en gietingspunte onveranderd gebly het. Die hipotese dat ‘n water wasstap na transesterifikasie tot swak kouevloei eienskappe lei is dus as onwaar bevind aangesien hierdie eienskappe deur die tipe biodiesel bepaal word. Deur ‘n hoogs versadigde biodiesel (lae aantal dubbelbindings) met ‘n minder versadigde biodiesel (hoë aantal dubbelbindings) te vermeng het tot ‘n verbetering van beide die vertroebelings- en gietingspunte gelei. / Centre for Renewable and Sustainable Energy Studies