Rozprawy doktorskie na temat „Biodiesel production from algae”

Driven by the rising costs, decreasing convenience, and increased demand of fossil fuels, the need for alternative, sustainable energy sources has caused a spark in interest in biomass-based fuels. Oleaginous organisms such as yeast, algae, and bacteria have been considered as microscopic biofactories for oils that can be converted into biodiesel. The process of growing such organisms using current technology requires an alarming amount of freshwater, which is another resource of growing concern. The research detailed within explains how several sources of underutilized wastewater can serve as growth medium in the biodiesel production process. Using only nitrogen and in one case phosphorus as external supplements, algae were shown to grow on produced water from oil and gas industry waste, local municipal wastewater, environmental brackish water from the Great Salt Lake, and wastewater from the potato processing industry. In each case, growth and biodiesel production in wastewaters was as good as or better than laboratory media. The bacterial organism Rhodococcus opacus PD630 and the yeast organism Cryptococcus curvatus were also used to grow on the dairy manufacturing wastewater whey permeate, a large source of underutilized fixed carbon, with successful lipid production. C. curvatus was also used to successfully grow and form large amounts of biodiesel from ice cream factory wastewater and from wheat straw hydrolysate. In each case, the need for freshwater and outside nutrients was nearly entirely replaced, with the exception of some nitrogen supplementation, with a wastewater nutrient source, thus adding to the sustainability of biomass-based fuels.

The aim of this study was to compare the production of biodiesel or biogas from macro algae harvested from the Baltic Sea from an energy perspective. The macro algae were considered to be harvested from an area along the southern coast of Sweden, between Malmö and Simrishamn. The gathering of algae is an attempt to reduce the current eutrophication in the Baltic Sea by removing nutrients that the algae have assimilated. The algae also contain some amounts of heavy metals, so the amounts of heavy metals in the marine environment are also reduced. The evaluation included all processes from harvesting of the algae, transport of the algae to the processing plants, processing of the algae to biodiesel or biogas.  An evaluation of the algae residues from the processes can be used as fertilizer in agriculture was also conducted. The inputs of materials and energy into the systems were calculated from values found in literature and estimated from similar studies. The evaluation method used was an emergy analysis where all the energy and material inflows into the processes were converted to solar emergy joules so the inflows can be compared on a common basis. The energy and material inflows into the system, including the harvesting, the transport and the biodiesel or biogas production processes, were converted with the use of transformities, which describes the amount of solar emergy joules per joule of energy, gram of material or cost in euro. The transformities for biodiesel and biogas were calculated and compared to give an indication of which product that is most efficient to produce. The processes were also evaluated using emergy indices, such as environmental loading ratio (ELR), emergy yield ratio (EYR), emergy sustainability index (ESI), emergy investment ratio (EIR) and percent renewability in the systems. The results of the study show that biogas has the lower transformity of the two, which means that the biogas production have utilized less solar emergy joules to produce 1 joule of energy than the biodiesel production. The total amount of solar emergy joules used per year for the biodiesel and biogas systems were calculated to 2.18·1019 seJ/year for biodiesel and 2.75·1019 seJ/year for biogas. The transformities calculated for biodiesel and biogas were 5.04·105 seJ/J and 9.12·104 seJ/J, respectively. The emergy indices, however, showed support for the biodiesel process by indicating lower environmental impacts, a higher economic competitiveness and a higher percent renewability.
Målet med studien var att utvärdera och jämföra processerna att tillverka biodiesel och biogas från alger skördade i Östersjön. Mängden av alger som kan skördas varje år har uppskattats till ungefär 215 000 ton våt vikt, på en yta mellan Malmö och Simrishamn längs med Sveriges sydkust. Algerna kan skördas mellan april och september. Insamlingen av alger har syftet att reducera den rådande övergödningen i Östersjön genom att ta upp näringsämnen som algerna har tillgodogjort sig. Algerna innehåller även tungmetaller som, när algerna samlas in, kan omhändertas och därmed minska mängderna tungmetaller i Östersjön. Utvärderingen inkluderade skörd av alger, transport av alger till biodiesel eller biogas anläggningen, tillverkning av biodiesel eller biogas och en utvärdering av algresterna efter processerna. Mängderna av energi och material som processerna konsumerar beräknades från litteraturvärden och uppskattades från liknande studier. Den utvärderingsmetod som användes var emergianalys, där all energi och material som har använts i systemen konverterades till ”solemergijoule” så att de kunde utvärderas utifrån en gemensam grund. De energier och material som används vid skörd och transport av alger och produktion av biodiesel eller biogas konverterades med hjälp av omräkningsfaktorer (Eng: ”transformities”) som beskriver förbrukningen av solemergijoule per energi i joule, material i gram eller kostnader i euro. De beräknade omräkningsfaktorerna/transformities för biodiesel och biogas användes i sin tur för att utvärdera vilken av processerna som kan anses mest effektiv. Utöver omräkningsfaktorerna/transformities användes även emergiindex som indikerar processernas påverkan på miljön, emergiutbyte, hållbarhet, ekonomisk konkurrenskraft och procent användning av förnyelsebara material- och energikällor. Resultatet av studien visade att biogas har en lägre omräkningsfaktor/transformity än biodiesel, vilket innebär att det har använts mindre solemergijoule för att tillverka 1 joule energi från biogas än för 1 joule biodiesel. Mängden solemergijoule som förbrukats per år uppskattades till 2.18·1019 seJ/år för biodiesel och 2.75·1019 seJ/år för biogas. Omräkningsfaktorerna/transformities beräknades för biodiesel och biogas till 5.04·105 seJ/J respektive 9.12·104 seJ/J. Emergiindex gynnade biodieselprocessen, då den visades ha en lägre påverkan på miljön, högre ekonomisk konkurrenskraft och en högre procentuell användning av förnyelsebara källor till material och energi som använts i processen.

With world crude oil reserves decreasing and energy prices continually increasing, interest in developing renewable alternatives to petroleum-based liquid fuels has increased. An alternative that has received consideration is the growth and harvest of microalgae for the production of biodiesel via extraction of the microalgal oil or lipids. However, costs related to the growth, harvesting and dewatering, and processing of algal biomass have limited commercial scale production of algal biodiesel. Coupling wastewater remediation to microalgal growth can lower costs associated with large scale growth of microalgae. Microalgae are capable of assimilating inorganic nitrogen and phosphorous from wastewater into the biomass. By harvesting the microalgal biomass these nutrients can be removed, thus remediating the wastewater. Standard methods of oil extraction require drying the harvested biomass, adding significant energetic cost to processing the algal biomass. Extracting algal lipids from wet microalgal biomass using traditional methods leads to drastic reductions in extraction efficiency, driving up processing costs. A wet lipid extraction procedure was developed that was capable of extracting 79% of the transesterifiable lipids from wet algal biomass (16% solids) without the use of organic solvents while using relatively mild conditions (90 °C and ambient pressures). Ultimately 77% of the extracted lipids were collected for biodiesel production. Furthermore, the procedure was capable of precipitating chlorophyll, allowing for the collection of algal lipids independently of chlorophyll. The capability of this procedure to extract lipids from wet algal biomass, to reduce chlorophyll contamination of the algal oil, and to generate feedstock material for the production of additional bio-products provides the basis for reducing scale-up costs associated with the production of algal biofuels and bioproducts.

Le sperimentazioni riguardanti la produzione di biodiesel da alghe sono state condotte solo in laboratorio o in impianti pilota e il processo produttivo non è ancora stato sviluppato su scala industriale. L’obiettivo di questo lavoro di tesi è stato quello di valutare la potenziale sostenibilità ambientale ed energetica della produzione industriale di biodiesel da microalghe nella realtà danese ipotizzando la coltivazione in fotobioreattori. La tesi ha analizzato le diverse tecnologie attualmente in sperimentazione cercando di metterne in evidenza punti di forza e punti di debolezza. La metodologia applicata in questa tesi per valutare la sostenibilità ambientale ed energetica dei processi analizzati è LCA strumento che permette di effettuare la valutazione sull’intero ciclo di vita di un prodotto o di un processo. L’unità funzionale scelta è 1 MJ di biodiesel. I confini del sistema analizzato comprendono: coltivazione, raccolta, essicazione, estrazione dell’olio, transesterificazione, digestione anaerobica della biomassa residuale e uso del glicerolo ottenuto come sottoprodotto della transesterificazione. Diverse categorie d’impatto sono state analizzate. In questo caso studio, sono stati ipotizzati 24 diversi scenari differenziati in base alle modalità di coltivazione, di raccolta della biomassa, di estrazione dell’olio algale. 1. la produzione di biodiesel da microalghe coltivate in fotobioreattori non appare ancora conveniente né dal punto di vista energetico né da quello ambientale. 2. l’uso di CO2 di scarto e di acque reflue per la coltivazione, fra l’altro non ancora tecnicamente realizzabili, migliorerebbero le prestazioni energetiche ed ambientali del biodiesel da microalghe 3. la valorizzazione di prodotti secondari svolge un ruolo importante nel processo e nel suo sviluppo su larga scala Si conclude ricordando che il progetto di tesi è stato svolto in collaborazione con la Danish Technical University of Denmark (DTU) svolgendo presso tale università un periodo di tirocinio per tesi di sei mesi

Algae have been the centre of recent research as a sustainable feedstock for fuel because of their higher oil yield in comparison to other plant sources. However, algae biofuel still performs poorly from an economic and environmental perspective due to the high reliance on freshwater and nutrients for cultivation, among other challenges. The use of wastewater has been suggested as a sustainable way of overcoming these challenges because wastewater can provide a source of water and nutrients for the algae. Moreover, the ability of the algae to remove contaminants from wastewater also enhances the total economic output from the cultivation. However, the success of this strategy still depends greatly on efficient strain selection, cultivation and harvesting. Therefore, this PhD thesis has focussed on strain isolation, characterisation, optimisation and cultivation in open pond systems. Five algae strains were isolated from wastewater treatment tanks at a municipal water treatment plant in North West England. The isolated strains were morphologically and genetically characterised as green single-celled microalgae: Chlamydomonas debaryana, Hindakia tetrachotoma, Chlorella luteoviridis, Parachlorella hussii and Desmodesmus subspicatus. An initial screening of these strains concluded that C. luteoviridis and P. hussii were outstanding in all comparisons and better than some of the strains previously reported in the literature. Further tests carried out to elucidate the underlying tolerance mechanisms possessed by these strains were based on stress tolerance and acclimation hypotheses. In the following experiments, C. luteoviridis and P. hussii were found to have higher anti-oxidant enzyme activity that helps in scavenging reactive oxygen species produced as a result of exposure to wastewater. This result provides a new argument for screening microalgae strains for wastewater cultivation on the basis of anti-oxidant activity. In addition, the two strains could grow heterotrophically and are better adapted to nutrient deficiency stress than the other three isolates. In order to understand the role of microalgae acclimation in wastewater cultivation, strains identical or equivalent to the wastewater treatment tank isolates were obtained from an algae culture collection. These strains had not been previously exposed to wastewater secondary effluent. The initial growth of these strains in wastewater secondary effluent was very poor. However, after two months of acclimation to increasing concentrations of secondary wastewater effluent, it was observed that growth, biomass and lipid productivities of most of the strains were significantly improved, although still not as high as the indigenous strains. Therefore, it was concluded that continuous acclimation is an additional factor to the successful growth of algae in wastewater. Furthermore, addition of 25% activated sludge centrate liquor to the secondary effluent was found to increase algal growth and biomass productivity significantly. Futher tests to examine the continous cultivation of C. luteoviridis and P. hussii in wastewater showed that a biomas productivity of 1.78 and 1.83 g L-1 d-1 can be achieved on a continual basis. Finally, the capability of C. luteoviridis and P. hussii for full seasonal cultivation in a 150 L open pond in a temperate climate was studied, using the optimised secondary wastewater +25% liquor medium. Each strain was capable of growth all year including in autumn and winter but with strongest growth, productivity and remediation characteristics in the summer and spring. They could maintain monoculture growth with no significant contamination or culture crash, demonstrating the robustness of these strains for wastewater cultivation in a northern European climate.

Renewable energy sources such as biomass are becoming more and more important as alternative to fossil fuels. One of the most exciting new sources of biomass is microalgae. The Hartbeespoort Dam, located 37 km west of South Africa’s capital Pretoria, has one of the dense populations of microalgae in the world, and is one of the largest reservoirs of micro-algal biomass in South Africa. The dam has great potential for micro-algal biomass production and beneficiation due to its high nutrient loading, stable climatic conditions, size and close proximity to major urban and industrial centres. There are five major steps in the production of biodiesel from micro-algal biomass-derived oil: the first two steps involve the cultivation and harvesting of micro-algal biomass; which is followed by the extraction of oils from the micro-algal biomass; then the conversion of these oils via the chemical reaction transesterification into biodiesel; and the last step is the separation and purification of the produced biodiesel. The first two steps are the most inefficient and costly steps in the whole biomass-to-liquids (BTL) value chain. Cultivation costs may contribute between 20–40% of the total cost of micro-algal BTL production (Comprehensive Oilgae Report, 2010), while harvesting costs may contribute between 20–30% of the total cost of BTL production (Verma et al., 2010). Any process that could optimize these two steps would bring a biomass-to-liquids process closer to successful commercialization. The aim of this work was to study the cultivation and harvesting of micro-algal biomass from the Hartbeespoort Dam for the production of biodiesel. In order to do this a literature study was done and screening experiments were performed to determine the technical and economical feasibility of cultivation and harvesting methods in the context of a new integrated biomass-to-liquids biodiesel process, whose feasibility was also studied. The literature study revealed that the cyanobacterium Microcystis aeruginosa is the dominant micro-organism species in the Hartbeespoort Dam. The study also revealed factors that promote the growth of this species for possible incorporation into existing and new cultivation methods. These factors include stable climatic conditions, with high water temperatures around 25oC for optimal Microcystis growth; high nutrient loadings, with high phosphorus (e.g. PO43-) and nitrogen concentrations (e.g. NO3-); stagnant hydrodynamic conditions, with low wind velocities and enclosed bays, which promote the proliferation of Microcystis populations; and substrates like sediment, rocks and debris which provide safe protective environments for Microcystis inoculums. The seven screening studies consisted of three cultivation experiments, three harvesting experiments and one experiment to determine the combustion properties of micro-algal biomass. The three cultivation experiments were conducted in three consecutively scaled-up laboratory systems, which consisted of one, five and 135-litre bioreactors. The highest productivity achieved was over a period of six weeks in the 5-litre Erlenmeyer bioreactors with 0.0862 g/L/d at an average bioreactor day-time temperature of 26.0oC and an aeration rate of 1.5 L/min. The three cultivation experiments revealed that closed-cultivation systems would not be feasible as the highest biomass concentrations achieved under laboratory conditions were too low. Open-cultivation systems are only feasible if the infrastructure already exists, like in the case of the Hartbeespoort Dam. It is recommended that designers of new micro-algal BTL biodiesel processes first try to capitalize on existing cultivation infrastructure, like dams, by connecting their processes to them. This will reduce the capital and operating costs of a BTL process significantly. Three harvesting experiments studied the technical feasibility and determined design parameters for three promising, unconventional harvesting methods. The first experiment studied the separation of Hartbeespoort Dam micro-algal biomass from its aqueous phase, due to its natural buoyancy. Results obtained suggest that an optimum residence time of 3.5 hours in separation vessels would be sufficient to concentrate micro-algal biomass from 1.5 to 3% TSS. The second experiment studied the aerial harvesting yield of drying micro-algal biomass (3% TSS) on a patch of building sand in the sun for 24 hours. An average aerial harvesting yield of 157.6 g/m2/d of dry weight micro-algal biomass from the Hartbeespoort Dam was achieved. The third experiment studied the gravity settling harvesting yield of cultivated Hartbeespoort Dam-sourced microalgae as it settles to the bottom of the bioreactor after air agitation is suspended. Over 90% of the micro-algal biomass settled to the bottom quarter of the bioreactor after one day. Cultivated micro-algal biomass sourced from the Hartbeespoort Dam, can easily be harvested by allowing it to settle with gravity when aeration is stopped. Results showed that gravity settling equipment, with residence times of 24 hours, should be sufficient to accumulate over 90% of cultivated micro-algal biomass in the bottom quarter of a separation vessel. Using this method for primary separation could reduce the total cost of harvesting equipment dramatically, with minimal energy input. All three harvesting methods, which utilize the natural buoyancy of Hartbeespoort Dam microalgae, gravity settling, and a combination of sand filtration and solar drying, to concentrate, dewater and dry the micro-algal biomass, were found to be feasible and were incorporated into new integrated BTL biodiesel process. The harvesting processes were incorporated and designed to deliver the most micro-algal biomass feedstock, with the least amount of equipment and energy use. All the available renewable power sources from the Hartbeespoort Dam system, which included wind, hydro, solar and biomass power, were utilized and optimized to deliver minimum power loss, and increase power output. Wind power is utilized indirectly, as prevailing south-easterly winds concentrate micro-algal biomass feedstock against the dam wall of the Hartbeespoort Dam. The hydraulic head of 583 kPa of the 59.4 meter high dam wall is utilized to filter and transport biomass to the new integrated BTL facility, which is located down-stream of the dam. Solar power is used to dry the microalgae, which in turn is combusted in a furnace to release its 18,715 kW of biochemical power, which is used for heating in the power-intensive extraction unit of the processing facility. Most of the processes in literature that cover the production of biodiesel from micro-algal biomass are not thermodynamically viable, because they consume more power than what they produce. The new process sets a benchmark for other related ones with regards to its net power efficiency. The new process is thermodynamically efficient, exporting 20 times more power than it imports, with a net power output of 5,483 kilowatts. The design of a new integrated BTL process consisted of screening the most suitable methods for harvesting micro-algal biomass from the Hartbeespoort Dam and combining the obtained design parameters from these harvesting experiments with current knowledge on extraction of oils from microalgae and production of biodiesel from these oils into an overall conceptual process. Three promising, unconventional harvesting methods from Brink and Marx (2011), a micro-algal oil extraction process from Barnard (2009), and a process from Miao and Wu (2005) to produce biodiesel through the acid-catalyzed transesterification of micro-algal oil, were combined into an integrated BTL process. The new integrated biomass-to-liquids (BTL) process was developed to produce 2.6 million litres of biodiesel per year from harvested micro-algal biomass from the Hartbeespoort Dam. This is enough to supply 51,817 medium-sized automobiles per year or 142 automobiles per day of environmentally friendly fuel. The new BTL facility consists of three sections: a cultivation section where microalgae grow in the 20 km2 Hartbeespoort Dam to a concentration of 160 g/m2 during the six warmest months of the year; a harvesting section where excess water is removed from the micro-algal biomass; a reaction section where fatty acid oils are extracted from the microalgae and converted to biodiesel, and dry biomass rests are combusted to supply heat for the extraction and biodiesel units of the reaction section. The cultivation section consist of the existing Hartbeespoort Dam, which make up the cultivation unit; the harvesting section is divided into a collection unit (dam wall part of the Hartbeespoort Dam), a concentration unit, a filtration unit, and a drying unit; the reaction section consists of an oil extraction unit, a combustion unit, and a biodiesel unit. At a capital cost of R71.62 million (R1.11/L) (±30%), the new proposed BTL facility will turn 933,525 tons of raw biomass (1.5% TSS) into 2,590,856 litres of high quality biodiesel per year, at an annual operating cost of R11.09 million (R4.28/L at 0% producer inflation), to generate R25.91 million (R10.00/L) per year of revenue. At the current diesel price of R10.00/L, the new integrated BTL process is economically feasible with net present values (NPV) of R368 million (R5.68/L) and R29.30 million (R0.45/L) at discount rates of 0% and 10%, respectively. The break-even biodiesel prices are R5.34/L and R7.92/L, for a zero NPV at 0% and 10% discount rates, respectively. The cultivation of micro-algal biomass from the Hartbeespoort Dam is only economical if the growth is allowed to occur naturally in the dam without any additional cultivation equipment. The cultivation of micro-algal biomass in either an open or a closed-cultivation system will not be feasible as the high cost of cultivation will negate the value of biodiesel derived from the cultivated biomass. The utilization of the three promising harvesting methods described in this work is one of the main drivers for making this process economically feasible. At a capital cost of R13.49 million (R37.77/ton of dry weight micro-algal biomass) and a operating cost of R2.00 million per year (R210.63/ton of dry weight micro-algal biomass) for harvesting micro-algal biomass from the Hartbeespoort Dam, harvesting costs account for only 19% and 18% of the overall capital and operating costs of the new process, respectively. This is less than harvesting costs for other comparative processes world-wide, which contribute between 20 and 30% of the overall cost of biomass-to-liquids production. At current fuel prices, the cultivation of micro-algal biomass from and next to the Hartbeespoort Dam is not economical, but the unconventional harvesting methods presented in this thesis are feasible, if incorporated into the new integrated biomass-to-liquids biodiesel process set out in this work.
Thesis (Ph.D. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2011.

We explored using de-oiled algal biomass (algal cake) as a low-value substrate for production of lactic acid in fermentations with Lactobacillus casei, and strategies for increasing lactic acid production at low pH. L. casei 12A algal cake (AC) fermentations showed carbohydrate and amino acid availability limit growth and lactic acid production. These nutritional requirements were effectively addressed with enzymatic hydrolysis of the AC using α-amylase, cellulase, and pepsin. Producing 0.075 g lactic acid per g AC from AC digested with all three enzymes. We explored heterologous expression of the cellulase gene (celE) from Clostridium thermocellum and the α-amylase gene (amyA) from Streptococcus bovis in L. casei 12A. Functional activity of CelE was not detected, but low-level activity of AmyA was achieved, and increased > 1.5-fold using a previously designed synthetic promoter. Nonetheless, the improvement was insufficient to significantly increase lactic acid production. Thus, substantial optimization of amyA and celE expression in L. casei 12A would be needed to achieve activities needed to increase lactic acid production from AC. We explored transient inactivation of MutS as a method for inducing hypermutability and increasing adaptability of L. casei 12A and ATCC 334 to lactic acid at low pH. The wild type cells and their ΔmutS derivatives were subject to a 100-day adaptive evolution experiment, followed by repair of the ΔmutS lesion in representative isolates. Growth studies at pH 4.0 revealed that all four adapted strains grew more rapidly, to higher cell densities, and produced significantly more lactic acid than untreated wild-type cells. The greatest increases were observed from the adapted ΔmutS derivatives. Further examination of the 12A adapted ΔmutS derivative identified morphological changes, and increased survival at pH 2.5. Genome sequence analysis confirmed transient MutS inactivation decreased DNA replication fidelity, and identified potential genotypic changes in 12A that might contribute to increased acid lactic acid resistance. Targeted inactivation of three genes identified in the adapted 12A ΔmutS derivative revealed that a NADH dehydrogenase (ndh), phosphate transport ATP-binding protein PstB (pstB), and two-component signal transduction system (TCS) quorum-sensing histidine kinase (hpk) contribute to increased acid resistance in 12A.

Le microalghe rappresentano una risorsa naturale per la produzione di biocombustibili i quali si rendono oggigiorno necessari per garantire sostenibilità energetica al pianeta dato il diminuire delle risorse fossili. Tuttavia il costo alla pompa di 1 litro di “algaediesel” oggi sarebbe di oltre 2,5$. Pertanto la diminuzione del suo costo è primario per poter affermare una delle tecnologie rinnovabili più promettenti del secolo attuale: di fatti le microalghe sintetizzano CO2 tramite fotosintesi ed hanno tassi di crescita spaventosamente veloci se confrontati con le tradizionali colture terrestri. Lo sforzo scientifico è quello di poter intervenire efficientemente in tutte le fasi coinvolte nel processo: dalla selezione di nuovi ed interessanti ceppi microalgali fino alla ottimizzazione del profilo lipidico ottenibile con la loro crescita. In questo lavoro si è cercato di evidenziare questi aspetti cruciali quali l’importanza della produttività lipidica, la sua stabilità e la possibilità di integrazione tecnologica tramite l’uso di un mezzo di crescita costituito da un refluo zootecnico proprio perché il mezzo di crescita è una delle voci di costo più elevate. Gli esperimenti hanno mostrato che: nuovi ceppi oleaginosi di microalghe con %lipidi per DW (>20%) possono ancora essere scoperti ed ottimizzati nella crescita; che un processo di produzione di biodiesel non può prescindere da biomassa con produttività e profilo lipidico stabile durante la fase di raccolta e che un refluo zootecnico, può essere un ottimo substrato di crescita per un ceppo “dominante” di microalghe soprattutto se vengono aggiustate le sue condizioni di crescita. Infine si è proposto un metodo per efficiente l’attuale processo industriale di biodiesel tramite con un approccio multiobiettivo, il quale ha permesso un risparmio termico del 13%.
Microalgae represent a natural resource to produce third generation biodiesel which is going to be necessary due to the shortening of the fossil resources. However, the actual cost of one litre of "algaediesel" would be higher than 2.5$. Therefore, the reduction of the costs connected with its production is primary to be make feasible one of the most promising renewable technologies of the century. Microalgae synthesize CO2 through photosynthesis growing much faster than traditional crop. The research is nowadays focused on efficiently improve of all the steps involved in the process: from the selection of new and interesting algal strains to the optimization of lipid profile obtainable from their cultivation. In this work, we tried to highlight and analyse important threads such as lipid productivity, lipids stability and productivity during continuous culture and the opportunity of integrate the wastewater treatment with the needing of lower the price of the growing substrate. The experiments show that new oleaginous strains with % of lipids in DW higher than 20% are easily discoverable and they will need a complete investigation on the optimization of the growth. They also show that the biodiesel production process cannot be separated from biomass productivity and lipid profile stability during the harvest of the biomass. Moreover, we show how a wastewater can be an excellent growth substrate "dominant" microalgae strain which can grow with good performances in a waste lowering the money necessary for the cultivation. Finally, we proposed a method for efficiently optimize the thermal needing of a real biodiesel plant by a multi-objective approach which allow saving of 13% of the thermal requirement.

As the global population rises to an estimated 9.4bn by 2050, the pressure for food, fuel and freshwater will continue to increase. Current renewable energy technologies are not widely applicable to the transport sector, which requires energy dense liquid fuels that drop into our existing infrastructure. Algal biofuels promise significantly higher yields than plants, without the displacement of valuable agricultural resources and have the potential to meet the global demand for transport fuel. Fossil fuel energy is largely ‘a legacy of algal photosynthesis’, with algae accounting for ~50% of global CO2 fixation today. In addition, these curious organisms show remarkable diversity in form, behaviour and composition. Recently there has been a global resurgence of interest in microalgae as a resource of biomass and novel products. With the present level of technology, knowledge and experience in commercial scale aquaculture, the capital cost and energy investment for algal biomass production is high. Culturing, harvesting and disrupting microalgal cells account for the largest energy inputs with more positive energy balances requiring low energy designs for culture, dewatering and extraction, efficient water and nutrient recycling with minimal waste. Little is known about the variable cell wall of microalgae, which presents a formidable barrier to the extraction of microalgal products. Staining, transmission electron microscopy (TEM) and enzymatic digestion were all utilised in an attempt to visualise, digest and characterise the cell wall of stock strains of Chlorella spp. and Pseudochoricystis ellipsoidea. The presence of algaenan, a highly resistant biopolymer, rendered staining and enzymatic digestion techniques ineffective. TEM revealed that algaenan is present in the outer walls of microalgae in a variety of conformations which appeared to impart strength to cells. A preliminary investigation utilising Fusarium oxysporum f.sp. elaeidis as a novel source of enzymes for the digestion of algaenan has also been described. Methods were developed for the mutagenesis of Chlorella emersonii and P. ellipsoidea using EMS and UV with the intent of generating cell-wall mutants. Although no viable cell wall mutants were produced, a viable pale mutant of C. emersonii was recovered 5 from UV mutagenesis. Growth rates of the pale mutant were significantly slower than the wild type, yet FAME profile was largely unaffected. Fluorescence activated cell sorting (FACS) was also investigated as a means for the rapid screening of mutagenized cells for cell wall mutants. In an attempt to reduce cooling costs of closed-culture systems, temperature tolerant species of microalgae were sought by bioprospecting the thermal waters of the Roman Baths. Numerous methods for isolation and purification of microalgae from the Baths were employed, ultimately yielding seven diverse isolates including cyanobacterial, eukaryotic, filamentous and single celled species. Despite some species possessing an increased tolerance to higher temperatures, none showed marked temperature tolerance coupled with high productivity. Further improvements to the culture conditions may have improved the productivity at higher temperatures. All seven isolates were deposited to the Culture Collection of Algae and Protozoa (CCAP). A variety of extraction methods including soxhlet, beadbeating, sonication and microwaving was investigated for efficacy of extracting fatty acid methyl esters (FAMEs) from C. emersonii. Beadbeating proved most effective in the extraction of FAMEs from C. emersonii. Microwaving showed potential as a rapid method of extraction yet was coupled with degradation of FAMEs, requiring further method development to resolve this issue. Method development has been a significant component of the work described in this thesis.

Hydrolysis, esterification and transesterification reactions were conducted in different reactor configurations, with the overall objective of enhancing the fundamental knowledge of Free Fatty acids (FFA) and biodiesel production, while providing key processing parameters and kinetic models for process design. Hydrolysis and esterification reactions were conducted in a non-catalytic continuous flow reactor, esterification reactions in a stirred batch reactor and transesterification reactions in a state-of-the-art Downflow Gas contactor Reactor (DGCR). The DGCR was operated in batch mode with a recycle loop. All samples were collected as a function of time and the concentrations of FFA and Fatty Acid Methyl/Ethyl Esters (FAME/FAEE) were determined, using gas chromatography for FFA and FAME/FAEE and titration for FFA. Tested processing variables for each reaction were varied according to the reaction objectives and reactor limits. Extensive kinetic models for continuous flow and batch reactions were performed and rate constants were established. FFA are an important intermediate for several industrial applications. Non-catalytic continuous flow hydrolysis with the aid of subcritical water produced high quality FFA with a maximum yield of 92 % at 350 \(^0\)C, 20 MPa and 50:50 water oil volume ratio. Temperature, time and water/oil initial ratio were found to be significant factors in the hydrolysis reactions. However, pressure had a minor influence.

This project investigates the potential of the 27 Everglades green algal strains for producing biodiesel. The five potential strains chosen by measuring the neutral lipid content using the Nile red method were Coelastrum 46-4, Coccoid green 64-12, Dactylococcus 64-10, Stigeoclonium 64-8 and Coelastrum 108-5. Coelastrum 108-5 and Stigeoclonium 64-8 yielded the same amount of lipids in both Gravimetric and Nile red method. A linear relationship between algal biomass and lipid accumulation was seen in Coelastrum 46-4, Coccoid green 64-12, Stigeoclonium 64-8 and Coelastrum 108-5 indicating that increase in algal biomass increased the lipid accumulation. Nitrogen and phosphorous stress conditions were also studied where higher lipid accumulation was observed significantly (p < 0.05) in 64-8 Stigeoclonium and 64-12 Coccoid green. Collectively, it could be summarized that Coelastrum 108-5, Coccoid green 64-12 and Stigeoclonium 64-8 were promising in some aspects and could be used for further studies.

This research has been directed at furthering the utilization of crude glycerol oversupply formed as a by-product from the biodiesel manufacturing process. Phosphorylation of hydroxyl groups is a synthetic route that was investigated for the conversion of glycerol into a glycerol-phosphate (GPE) ester mixture. The process investigated for the synthesis of a GPE product was based on phosphorylation reaction procedures that were previously reported in the literature. The reaction to convert glycerol into a GPE mixture has been thoroughly investigated and the hydrogen chloride gas formed as a reaction by-product has been optimized. The chemical properties of GPE have been studied and discussed together with a mass balance of the overall glycerol phosphorylation process. The phosphate groups contained in polyhydric phosphate molecules have a potential chelating effect on cations. There are several cations that may be chelated by the phosphate ester group of polyhydric phosphate molecules. These cations include ammonium (NH4+), Potassium (K+), Calcium (Ca2+) etc, which are essential as nutrients in plant fertilizer formulations. This research has investigated the use of a GPE synthesized from glycerol in the laboratory and the use thereof as a phosphorus containing base in the formulation and evaluation of Nitrogen, Phosphorus and Potassium (NPK) containing fertilizer solution, Ammonium-Potassium-Glycerol-Phosphate (APGP) fertilizer solution. The APGP fertilizer solution has further been evaluated by growing two week old tomato seedlings under controlled conditions. The performance of the APGP fertiliser solution has been evaluated using design of experiments by comparison with traditionally used liquidAmmonium-Potassium-Phosphate inorganic fertilizer. This fertilizer solution has been prepared in similar manner as APGP formulation with the difference between them being the source of phosphorus. The results have been evaluated using statistic analysis where a significant difference between the evaluated fertilizer formulations was found. The comparative study of these formulations was monitored by the observed plant weights. A blank treatment was used as a control to determine if a significant difference among these formulations was observed. Anova single factor and t-Test methods (Two-Samples assumed of equal variances) are statistical models that were applied to interpret the observed experimental data with respect to wet and dry weighed masses of tomato seedlings. These methods indicated a confirmed conclusion that there was a significant difference between APPO4 solution and APGP solution. The observed data have shown that the APPO4 solution provided significantly better fertigation performance than APGP solution. Consequently, further investigation has been conducted to determine the cause of the poorer performance of the APGP solution. The further study of the APGP fertilizer solution included nutrient stability testing, biological analysis and other observed physical changes of the APGP solution over time. Biological results have revealed the presence of a Fusarium fungus species that has grown and is suspended in APGP fertilizer solution. This microbe species has been observed to play a vital role in consuming fertilizer nutrients. In addition, the observed abnormal plant growth and nutrient decomposition of the APGP formulation has been proposed to be mostly a result of the pathogenicity of the fusarium fungi species that was suspended in the APGP solution. Further work has been proposed in which the effect of such biological contamination is eliminated through adequate sterilization procedures and the APGP formulation re-evaluated.

The production of biodiesel using vegetables oils is studied. Palm oil and its use for production of biodiesel have been focused. Palm tree is very productive and one of the most profitable for biodiesel production. Among the oilseed crops palm tree produce more oil per hectare. Palm oil has a good availability and a competitive price. The production of palm oil at the industrial plantation level has caused environmental damage. The Roundtable on Sustainable Palm Oil has established principles and criteria in order to certify a sustainable cultivation of the palm oil. The experimental work involves the production of biodiesel using corn oil. Ethanol and methanol are used as alcohols. Sodium and potassium hydroxides are selected as catalyst. The ratio alcohol to oil is the most important parameter in the production of biodiesel.  An excess of alcohol is required to drive the reaction to the right.  In the experiments with ethanol the yield of biodiesel increased with the ratio ethanol/oil achieving the highest yield at a molar ratio ethanol/oil: 7.78. In the experiments with methanol, using 0.9 g NaOH and 1 hour reaction time the highest yield was obtained with  a molar ratio methanol:oil = 9. Using KOH as catalyst and 2 hour reaction time a very good yield is already obtained with a molar ratio methanol:oil = 4.5 The amount of catalyst is another studied parameter. In the experiments with ethanol, the amount of 0.8 mg NaOH and 1.2 mg KOH for 200 ml corn oil (0.22 mol) is enough in order to obtain a good yield. An increase of the amount of catalyst does not produce an increase of the yield of biodiesel. In experiments with methanol, using the lowest tested amount catalyst (0.85 g KOH and 0.23 g NaOH) a good yield of biodiesel is obtained. The effects of the reaction time, rate of mixing and the reaction temperature were studied in the experiments with methanol. The yield of biodiesel increased when the reaction time is increased from 1 to 2 hours. The yield of produced biodiesel increased from 90% to 94% when the rate of mixing was increased from 500 to 1500 rpm. Often the transesterification is carried out at a temperature near the boiling point of alcohol. The highest yield was obtained at 60 oC with KOH and at 55 oC using NaOH but already at 40 oC a good yield was obtained (89%).

Seaweed biomass has been identified as a potential fermentation substrate for third generation biofuel processes due to its high carbohydrate content and its potential for mass cultivation without competing for agricultural land, fresh water and fertilisers. This thesis aimed to develop and advance existing processes to convert brown seaweeds into bioethanol. The main kelp species chosen as biomass candidates were Laminaria digitata, Laminaria hyperborea, Saccharina latissima and Alaria esculenta due to their abundance in Scottish waters and their identified potential for mariculturing. These kelp species were chemically characterised to identify seasonal variations, to recommend suitable seaweed candidates for bioethanol production and predict best harvest times. This has only been demonstrated before on one species - L. digitata. The chemical composition analyses were carried out over a 14 months sampling period, which focused on the storage carbohydrates laminarin and mannitol and the structural carbohydrates alginate, cellulose, fucoidan and xylose. In addition to carbohydrates the protein, nitrogen, carbon, polyphenol, ash and metal content was also profiled. Chemical profiling identified all four kelps as potential fermentation candidates, where maximum carbohydrate contents coincided with lowest ash and polyphenol content, usually seen in autumn. Biomass pre-treatment and saccharification are up-stream processes aimed at enhancing extraction of carbohydrates and converting those into fermentable substrates. Conversion of seaweed biomass into fermentation substrate evaluated acids and enzymes for seaweed pre-treatment and saccharification. Methodologies focused on optimising saccharification yields were developed to identify process critical parameters and develop methods for routine analysis of seaweed biomass. Results demonstrated that dilute acid hydrolysis was were less effective in releasing fermentable sugars, and also resulted in higher salinities compared to enzymatic hydrolysis using hemicellulosic and cellulosic enzymes, which were the preferred method of saccharification. All seaweeds in this thesis were assessed as fermentation substrates using the yeasts S. cerevisiae and P. angophorae, that principally ferment glucose or mannitol, respectively. Small-scale fermentation assays were developed for both yeasts to maximise ethanol yields and achieve process robustness. Both yeasts achieved a maximum ethanol yield of 0.17 g g-1 using Laminaria spp. On the basis of results, S. cerevisiae is recommended as the most useful yeast at this present point for ethanol fermentation from seaweed hydrolysates because of its tolerance to high salinity and ethanol concentrations. As salinity can negatively affect non-halotolerant enzymes, isolation of marine microorganisms was therefore carried out with the aim to highlight their enzymatic potential in seaweed saccharification. This was achieved through the isolation of two members of the genus Pseudoalteromonas, where saccharification yields using crude intracellular enzyme preparations exceeded those of dilute acids. In addition, the fermentative potential of microbial isolates as future ethanologenic strains was also evaluated. Understanding of the metabolic pathways is needed to fully assess the potential of those strains for genetic alteration. In conclusion, this thesis has demonstrated that up to ca. 20 g l-1 of ethanol can be produced from kelp species that grow on the west coast of Scotland. The procedure developed and used to produce ethanol requires further development, specifically the need for ethanol-fermenting microorganisms that can utilize mannitol and alginate; use of marine-adapted enzymes for saccharifiction; and the development of processes to achieve substrate concentration with reduced salinities. Comparison of theoretical ethanol yields from seaweed biomass with ethanol yields from terrestrial crops showed that the complete utilisation of all three major seaweed carbohydrates (laminarin, mannitol and alginate) from kelp species is needed for the process to be able to compete with 1st generation biofuel processes.

Mestrado em Materiais Derivados de Recursos Renováveis
O ácido oleico é um co-produto da refinação de óleos alimentares e é removido num passo antecedente à catalise alcalina na produção industrial de biodiesel. Este ácido gordo livre é uma fonte alternativa de biodiesel. Neste trabalho estudou-se a esterificação enzimática do acido oleico com metanol ou etanol. Definiu-se um planeamento experimental 22 para estudar a influência das variáveis razão molar álcool/ácido oleico(R) e concentração de enzima(E), as variáveis dependentes, na percentagem de conversão, a variável independente. As condições óptimas foram obtidas em R=6,32 e E=6,64% para o metanol (100% conversão), e R=4,87 e E=5,65 % para o etanol (95,5% de conversão). Estudou-se também a influência da temperatura na reacção para uma razão molar de 6 e uma concentração de enzima de 2%, numa gama de temperaturas entre 30 e 60ºC, para o metanol, e 70ºC, para o etanol. Foi constatado que a conversão aumenta monotonamente com o aumento da temperatura para o etanol. Para o metanol, o aumento da conversão com o aumento da temperatura apenas se verifica até aos 50ºC. A mesma enzima pode ser usada 10 vezes na esterificação enzimática do ácido oleico com etanol, sem perda significativa de actividade enzimática. ABSTRACT: Oleic acid is a co-product of oil refining and is removed in a step preceding the alkaline catalysis in industrial production of biodiesel. This free fatty acid is an alternative source of biodiesel. In this present work the enzymatic esterification of oleic acid with methanol or ethanol was studied. Was defined as an design of experiments 22 to study the influence of the alcohol / oleic acid molar ratio (R) and enzyme concentration (E), the dependent variables, in the percentage of conversion, the independent variable The optimal conditions obtained were R=6.32 and E=6.64% for methanol (100% conversion), and R=4.87 and E=5.65% for ethanol (95,5% of conversion. Was also studied the influence of temperature on the reaction to a molar ratio of 6 and an enzyme concentration of 2%, in a temperature range between 30 and 60 ° C for methanol, and 70 ° C for ethanol. It was found that the conversion increases monotonously with increasing temperature for ethanol. For methanol, the conversion increased with increasing temperature up to 50 º C. The same enzyme can be used 10 times in the enzymatic esterification of oleic acid with ethanol, without significant loss of enzyme activity.

The goal of the project is to design a plant that is capable of converting an algae feedstock into compressed natural gas (CNG). This product is intended to be sold as a green replacement for CNG produced using traditional methods. In addition to CNG, hydrogen gas is produced; this product will be sold as a biofuel as well. The CNG produced in this process is created by gasifying algae in supercritical water and then reacting the algal matter over an Ru/C catalyst. The resulting gas is then purified and compressed to produce CNG and hydrogen. A process hazard analysis was conducted to identify and help reduce safety and environmental hazards. An economic analysis showed that the plant's net present value is ($37.5 million); therefore, it was not recommended that the plant be built at this time. Future work includes developing a cheap Ru/zirconia catalyst to replace the expensive Ru/C catalyst currently used in the process. Designs for vessels containing supercritical fluids should also be evaluated to find ways to minimize purchase and installation cost. In addition, pilot scale testing of specific pieces of equipment is required to ensure innovations included in the design function as expected.

Because of the depletion of the world’s petroleum reserves and the increasing environmental concerns, biodiesel, as a low-emission renewable fuel and one of the best substitutes for petro-diesel fuel, has attracted great public interest over the past decades. At present, camelina oil has been considered as a low-cost feedstock for biodiesel production because of its high oil content and environmental benefits. In the present study, the optimization of biodiesel production and purification from camelina oil is studied extensively in order to maximize the biodiesel yield. The orthogonal array design is used to optimize the biodiesel production and four relevant process conditions for affecting biodiesel yield are investigated: methanol to oil ratio, catalyst concentration, reaction time and temperature. For the optimization study on biodiesel purification, five commonly used washing methods are also investigated: cold deionized water washing, hot deionized water washing, phosphoric acid washing, ultrasonic assisted washing, and magnesol washing. The optimization study, based on traditional mechanical stirring process, reveals that the decreasing ranking of significant factors for biodiesel production is catalyst concentration > reaction time > reaction temperature > methanol to oil ratio. The maximum biodiesel yield is found at a molar ratio of methanol to oil of 8:1, a reaction time of 70 min, a reaction temperature of 50℃, and a catalyst concentration of 1 wt.%. After testing the fuel properties of the final product, the optimized biodiesel meets the relevant requirements of the biodiesel standards and thus can be used as a qualified fuel for diesel engines. The optimization study, based on ultrasonic-assisted transesterification process, reveals that the maximal fatty acid methyl ester yield of the final biodiesel product is obtained under a methanol to oil molar ratio of 8:1, catalyst concentration of 1.25 wt.%, reaction time of 50 min and reaction temperature of 55 ℃. Compared with traditional mechanical stirring production process, ultrasonic-assisted transesterification process improves the biodiesel production since it could reduce the production cost and save energy. For the optimization study on biodiesel purification, the fatty acid methyl ester yield of the final biodiesel product, energy consumption and economic costs of different washing methods are compared. The comparisons indicate that the ultrasonic assisted washing method is the best method for biodiesel purification, when energy consumption and operation costs are considered. A preliminary kinetics study of transesterification reaction of camelina oil is carried out. After discussing four cases for overall reaction, a third-order reaction mechanism was proposed to fit the experimental data better because of the highest coefficient of determination. Based on the best-fit plot, the rate constants and activation energy are also determined. To sum up, the present research focuses on the optimization of biodiesel production and purification from camelina oil, and provides insights into the optimal process conditions for maximizing the biodiesel yield. Further research works are finally recommended to be continued.
published_or_final_version
Mechanical Engineering
Doctoral
Doctor of Philosophy

The increase of petroleum cost as well as global warming and climate change result in investigation to discover new renewable energy resources. Bioenergy is one of the most important sources that is concerning the scientists and industrial sector. Although bioethanol had to be known as one of the most important renewable energy sources in order to reduce greenhouse gases and global warming, there is a limited number of publications reporting on them. In this review, a brief overview is offered about bioethanol production from algae. It can be given a deeper insight in dificulties and promising potential of bioethanol from algae
Sự gia tăng giá nhiên liệu hóa thạch cùng với cảnh báo toàn cầu về biến đổi khí hậu hướng đến việc nghiên cứu tìm ra những nguồn năng lượng có thể tái tạo. Năng lượng sinh học là một trong những nguồn quan trọng được các nhà khoa học và doanh nghiệp quan tâm. Mặc dù ethanol sinh học đã được biết đến như là một trong những dạng năng lượng tái tạo quan trọng nhất để giảm thiểu các khí nhà kính và cảnh báo toàn cầu, nhưng chỉ có một số ít bài báo về nó. Trong bài tổng quan này, chúng tôi giới thiệu vắn tắt việc sản xuất ethanol sinh học từ tảo. Nó đưa ra cái nhìn sâu hơn về những khó khăn và tiềm năng hứa hẹn của sản xuất ethanol sinh học từ tảo

The slow yet steady expansion of the global economies, has led to an increased demand for energy and fuel, which would eventually lead to shortage of fossil fuel resources in the near future. Consequently, researchers have been investigating other fuels like biodiesel. Biodiesel refers to the monoalkyl esters which can be derived from a wide range of sources like vegetable oils, animal fats, algae lipids and waste greases. Currently, biodiesel is largely produced by the conventional route, using an acid, a base or an enzyme catalyst. Drawbacks associated with this route result in higher production costs and longer processing times. Conversely, supercritical transesterification presents several advantages over conventional transesterification, such as, faster reaction rates, catalyst free reaction, less product purification steps and higher yields. This work focused on the supercritical transesterification of cooking oil, soybean in particular. The experimental investigation was conducted using methanol at supercritical conditions. These conditions were milder in terms of pressure than those reported in literature. A batch setup was designed, built and used to carry out the supercritical transesterification reactions. The biodiesel content was analyzed using gas chromatography-mass spectrometry to calculate reaction yields. Methyl ester yield of 90% was achieved within 10 minutes of reaction time using supercritical transesterification. A maximum yield of 97% was achieved with this process in 50 minutes of reaction time. Two key factors, temperature and molar ratio were studied using variance analysis and linear regression and their significance on the biodiesel yield was determined. The kinetic tendency of the reaction was investigated and the values of rate constants, activation energy and the pre-exponential factor were estimated.

Biodiesel, a transesterified product of vegetable oil and animal fats, is considered as the most promising diesel fuel substitute because of its similar properties to petroleum-based diesel fuel. In this thesis, the miscibility of canola oil and fatty acid methyl esters (FAME or biodiesel) in methanol was determined. Results showed that FAME is miscible in pure methanol under a broad range of conditions. On the other hand, canola oil is not miscible in methanol under normal conditions. These findings led to the development of a two-phase membrane reactor to produce FAME from canola oil and methanol. The transesterification of canola oil was performed via both acid- or base-catalysis. The novel reactor enabled the separation of a FAME and methanol solution from canola oil/methanol/FAME mixtures. The two-phase membrane reactor was particularly useful in removing unreacted canola oil from the FAME product yielding high purity biodiesel. A kinetic study of the acid- and base-catalyzed transesterification of canola oil to FAME was carried out to investigate reaction rates under different temperatures and catalyst concentrations in the two-phase membrane reactor. Results showed that increases in temperature, acid concentration and feedstock (methanol/oil) flowrate significantly increased the conversion of oil to biodiesel. However, the base-catalyzed reaction resulted in the production of soaps and slight damage to the carbon membrane used in the reactor. The kinetics of the reaction were more sensitive to temperature at high acid concentration.

The production of biodiesel from a butter factory effluent was the main focus of the study. The alkali transesterification reaction was used to produce the biodiesel. The effect of the temperature, alcohol to oil molar ratio, catalyst concentration and the reaction time was investigated to determine the optimal reaction conditions. The reaction temperature varied from 45 °C to 65 °C with a 5 °C increment. The alcohol to oil molar ratio varied from 3:1 to 8:1 with an increment of 1:1. The experiments with varying catalyst load were carried out at 0.8 wt%, 1.0 wt% and 1.2wt%. The reaction time was kept constant at 120 minutes, but samples of the reaction mixture were taken at 10 minute intervals. The optimal reaction conditions according to the results were 50 °C, 6:1 alcohol to oil molar ratio, 1.0 to 1.2 wt% catalyst loads and a reaction time of 60 to 90 minutes. The optimal temperature was also the maximum temperature since a further increase in temperature lowered the ester content. Increasing the alcohol to oil molar ratio above 6:1 had no effect on the ester content. The increase in catalyst load decreased the time needed for the reaction to reach equilibrium. The purification process was also investigated. The biodiesel was washed with water, Magnesol® DSOLTM and Purolite® PD-206. The Magnesol® D-SOLTM was the best method for lowering the water content and the acid value of the fuel. A Magnesol® D-SOLTM content of 1.0 wt% was mixed with the biodiesel for 30 minutes in order to lower the water content and the acid value to below the maximum limit. A kinetic model for the biodiesel reaction was developed. The model was based on the second order reversible reaction. The temperature range for the model is from 45 °C to 55 °C. The forward reaction was found to be exothermic with an endothermic reverse reaction. The activation energy for the exothermic forward reaction varied between 9.478 and 26.937 kJ/mol while the activation energy for the endothermic reverse reaction varied between 74.161 and 136.433 kJ/mol for the reactions with a catalyst load of 1.2 wt%. The biodiesel was tested according to the SANS 1935:2011 standard. The biodiesel did not meet all the requirements of the standard. The flash point, sulphur content, carbon residue, oxidation stability, free glycerol, total glycerol and cold filter plugging point did not meet the specification of SANS 1935:2011. The biodiesel should be blended with mineral diesel if it is to be used commercially. The butter factory effluent can be used as a feedstock for the production of biodiesel.
Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013.

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
FUNDAÇÃO DE APOIO A PESQUISA DA BAHIA
A busca pelo desenvolvimento sustentável tem como importante fator diferencial as fontes de energia renováveis. O biodiesel desponta como uma das alternativas mais relevantes, mas suas formas de obtenção no Rio de Janeiro não foram suficientemente investigadas. Este trabalho identifica a oportunidade da produção de biodiesel a partir de óleos residuais de fritura neste cenário, enfatizando os custos de transporte do óleo desde os principais produtores comerciais até a obtenção do biocombustível. O objetivo é avaliar os custos de forma a verificar a viabilidade do emprego desta alternativa. Para tanto, foram estudadas as diversas ferramentas de resolução do Problema de Roteamento de Veículos e foi proposto um algoritmo que visa à otimização dos custos. A formulação matemática utilizada baseia-se numa extensão de algoritmos clássicos, como o apresentado por Arenales et al. (2007), e nas equações desenvolvidas em Kallehauge (2006). Os resultados do modelo de roteamento, atrelados aos custos de produção, impostos e insumos, foram comparados com informações sobre a comercialização do biodiesel, comprovando sua viabilidade econômica. A consolidação dos dados obtidos aponta a produção de biodiesel a partir de óleo residual de fritura como viável, com custos logísticos equivalentes a R/tmp/aaaUFg8ya,19 por litro e custo final de R,22 por litro.
The search for a sustainable development has in renewable energy sources an important differential factor. Biodiesel is one of the most important alternatives, but its obtainment forms in Rio de Janeiro have not been investigated enough. This work identifies the opportunity of biodiesel production from waste cooking oil in this scenery, emphasizing oil`s transport costs until factories, where it is possible to obtain biodiesel in its final form. The objective is to evaluate costs in order to verify viability of this alternative source of energy. Hence, this research analysed several tools for solving Vehicle Routing Problem and it proposes an algorithm that results in cost optimization. The adapted mathematic formulation is based in an extension of classic algorithms, like those presented by Arenales (2007), and in equations developed by Kallehauge (2006). The routing model results, linked to production, tributes and input costs, have been compared with information about biodiesel commercialization, verifying its economic viability. The data consolidation obtained indicates that the biodiesel production from waste cooking oil is viable, with logistic costs equal to R/tmp/aaaPLIh7a,19 per liter and final cost equal to R,22 per liter.

1. Introduction Biodiesel (BD) is a liquid biofuel that is defined as a fatty acid methyl ester fulfilling standards such as the ones set by European (EN 14214) and the American (ASTM 6751) regulations. BD is obtained by the transesterification (Scheme 1.1) or alcoholysis of natural triglycerides contained in vegetable oils, animal fats, waste fats and greases, waste cooking oils (WCO) or side-stream products of refined edible oil production with short-chain alcohols, usually methanol or ethanol and using an alkaline homogeneous catalyst (Perego and Ricci, 2012). Scheme 1.1. Transesterification reaction. BD presents several advantages over petroleum-based diesel such as: biodegradability, lower particulate and common air pollutants (CO, SOx emissions, unburned hydrocarbons) emissions, absence of aromatics and a closed CO2 cycle. Refined, low acidity oilseeds (e.g. those derived from sunflower, soy, rapeseed, etc.) may be easily converted into BD, but their exploitation significantly raises the production costs, resulting in a biofuel that is uncompetitive with the petroleum-based diesel (Santori et al., 2012; Lotero et al., 2005). Moreover, the use of the aforementioned oils generated a hot debate about a possible food vs. fuel conflict, i.e. about the risk of diverting farmland or crops at the expense of food supply. It is so highly desirable to produce BD from crops specifically selected for their high productivity and low water requirements (Bianchi et al., 2011; Pirola et al., 2011), or from low-cost feedstock such as used frying oils (Boffito et al., 2012a) and animal fats (Bianchi et al., 2010). The value of these second generation biofuels, i.e. produced from crop and forest residues and from non-food energy crops, is acknowledged by the European Community, which states in its RED directive (European Union, RED Directive 2009/28/EC): ‘‘For the purposes of demonstrating compliance with national renewable energy obligations […], the contribution made by biofuels produced from wastes, residues, non-food cellulosic material, and ligno-cellulosic material shall be considered to be twice that made by other biofuels’’. However, the presence of free fatty acids in the feedstock, occurring in particular in the case of not refined oils, causes the formation of soaps as a consequence of the reaction with the alkaline catalyst. This hinders the contact between reagents and the catalyst and makes difficult the products separation. Many methods have been proposed to eliminate FFA during or prior to transesterification (Pirola et al., 2011; Santori et al., 2012). Among these the FFA pre-esterification method is a very interesting approach to lower the acidity since it allows to lower the acid value as well as to obtain methyl esters already in this preliminary step (Boffito et al., 2012a, 2012b; 2012c Bianchi et al., 2010, 2011; Pirola et al., 2010, 2011). Aims of the work The aims of this work are framed in the context of the entire biodiesel production chain, ranging from the choice of the raw material, through its standardization to the actual biodiesel production. The objectives can be therefore summarized as follows: Assessing the potential of some vegetable or waste oils for biodiesel production by their characterization, deacidification and final transformation into biodiesel; To test different ion exchange resins and sulphated inorganic systems as catalysts in the FFA esterification; To assess the use of ultrasound to assist the sol-gel synthesis of inorganic sulphated oxides to be used as catalysts in the FFA esterification reaction; To assess the use of sonochemical techniques such as ultrasound and microwave to promote both the FFA esterification and transesterification reaction. 2. Experimental details 2.1 Catalysts In this work, three kinds of acid ion exchange resins were used as catalysts for the FFA esterification: Amberlyst®15 (A15), Amberlyst®46 (A46) (Dow Chemical) and Purolite®D5081 (D5081). Their characteristic features are given in Tab. 2.1. Various sulphated inorganic catalysts, namely sulphated zirconia, sulphated zirconia+titania and sulphated tin oxide were synthesized using different techniques. Further details will be given as the results inherent to these catalysts will be presented. Catalyst A15 A46 D5081 Physical form opaque beads Type Macroreticular Matrix Styrene-DVB Cross-linking degree medium medium high Functional group -SO3H Functionalization internal external external external Form dry wet wet Surface area (m2 g-1) 53 75 514a Ave. Dp (Ǻ) 300 235 37a Total Vp (ccg-1) 0.40 0.15 0.47 Declared Acidity (meq H+g-1) 4.7 0.43 0.90-1.1 Measured acidity (meq H+g-1) 4.2 0.60 1.0 Moisture content (%wt) 1.6 26-36 55-59 Shipping weight (g l-1) 610 600 1310a Max. operating temp (K) 393 393 403 Tab. 2.1. Features of the ion exchange resins used as catalysts. The acidity of all the catalysts was determined by ion exchange followed by pH determination as described elsewhere (López et al., 2007; Boffito et al., 2012a; 2012b). Specific surface areas were determined by BET (Brunauer, Emmett and Teller, 1938) and pores sizes distribution with BJH method (Barrett, Joyner and Halenda, 1951). XRD, XPS SEM-EDX and HR-TEM analyses were performed in the case of catalysts obtained with the use of ultrasound (Boffito et al. 2012a). Qualitative analyses of Lewis and Brønsted acid sites by absorption of a basic probe followed by FTIR analyses was also carried out for this class of catalysts (Boffito et al, 2012a). 2.2 Characterization of the oils Oils were characterized for what concerns acidity (by acid-base titrations) as reported by Boffito et al. (2012a, 2012b; 2012c), iodine value (Hannus method (EN 14111:2003)), saponification value (ASTM D5558), peroxide value and composition by GC analyses of the methyl ester yielded by the esterification and transesterification. Cetane number and theoretical values of the same properties were determined using equations already reported elsewhere (Winayanuwattikun et al., 2008). 2.3 Esterification and transesterification reactions In Tab. 2.2, the conditions adopted in both the conventional and sonochemically-assisted esterification are reported. For all these experiments a temperature of 336 K was adopted. Vials were used to test the sulphated inorganic oxides, while Carberry reactor (confined catalyst) (Boffito et al., 201c) was used just for the FFA esterification of cooking oil. Rector oil (+ FFA) (g) MeOH (g) catalyst amount vial 21 3.4 5%wt/gFFA sulphated inorganic catalysts slurry 100 16 - 10 g ion exchange resins - 5%wt/gF FA sulphated inorganic catalysts Carberry 300 48 10 g (5 g in each basket) Tab. 2.2. Free fatty acids esterification reaction conditions for conventional and sonochemically-assisted experiments. All the sonochemically-assisted experiments were performed in a slurry reactor. FFA conversions were determined by acid-base titrations of oil samples withdrawn from the reactors at pre-established times and calculated as follows: "FFA conversion (%)=" (〖"FFA" 〗_"t=0" "-" 〖"FFA" 〗_"t" )/〖"FFA" 〗_"t=0" " x 100" In Tab. 2.3, the conditions of both the conventional and ultrasound (US)-assisted transesterification are reported. KOH and CH3ONa were used for conventional experiments, while just KOH for the US-assisted experiments. The BD yield was determined by GC (FID) analysis of the methyl esters. Method Reactor Step gMeOH/100 goil gKOH/100 goil Temp. (K) Time (min) traditional batch step 1 20 1.0 333 90 step 2 5.0 0.50 60 US-assisted batch step 1 20 1.0 313, 333 30 US-assisted continuos step 1 20 1.0 338 30 Tab. 2.3. Transesterification reaction conditions. 3. Results and Discussion 3.1 Characterization and deacidification of different oils by ion exchange resins: assessment of the potential for biodiesel production In Tab. 3.1 the results of the characterization of the oils utilized in this work are displayed. The value in parentheses indicate the theoretical value of the properties, calculated basing on the acidic composition. The acidity of all the oils exceeds 0.5%wt (~0.5 mgKOH/g), i.e. the acidity limit recommended by both the European normative (EN 14214) and American standard ASTM 6751 on biodiesel (BD). The iodine value (IV) is regulated by the EN 14214, which poses an upper limit of 120 gI2/100 g. The number of saturated fatty chains in the fuel determines its behaviour at low temperatures, influencing parameters such as the cloud point, the CFPP (cold filter plugging point) and the freezing point (Winayanuwattikun et al., 2008). The IV are in most of the cases similar to the ones calculated theoretically. When the experimental IV differs from the theoretical one, it is in most of the cases underestimated. This can be explained considering the peroxide numbers (PN), which indicates the concentration of O2 bound to the fatty alkyl chains and is therefore an index of the conservation state of oil. Oils with high IV usually have a high concentration of peroxides, whereas fats with low IV have a relatively low concentration of peroxides at the start of rancidity (King et al., 1933). Moreover, although PN is not specified in the current BD fuel standards, it may affect cetane number (CN), a parameter that is regulated by the standards concerning BD fuel. Increasing PN increases CN, altering the ignition delay time. Saponification number (SN) is an index of the number of the fatty alkyl chains that can be saponified. The long chain fatty acids have a low SN because they have a relatively fewer number of carboxylic functional groups per mass unit of fat compared to short chain fatty acids. In most of the cases the experimental SN are lower than the ones calculated theoretically. This can be explained always considering the PN, indicating a high concentration of oxygen bound to the fatty alkyl chains. Oil Acidity (%wt) IV1 (gI2/ 100 g) PN2 (meqO2 /kg) SN3 (mg KOH/g) CN4 Fatty acids composition (%wt) animal fat (lard)* 5.87 51 2.3 199 62.3 n.d. soybean* 5.24 138 3.8 201 42.4 n.d. tobacco1 1.68 143 (149) 21.9 199 (202) 41.6 (39.8) C14:0 (2.0) C16:0 (8.3) C18:0 (1.5) C18:1 (12.0) C18:2 (75.3) C18:3 (0.6) C20:0 (0.1) C22:0 (0.2) sunflower* 3.79 126 3.7 199 45.4 n.d. WSO5 0.50 118 (129) 71.3 187 (200) 48.9 (44.6) C16:0 (6.9) C18:0 (0.9) C18:1 (40.1) C18:2 (50.9) C18:3 (0,3) C20:0 (0.1) C20:1 (0.4) C22:0 (0.4) palm 2.71 54.0 (53.0) 12.3 201 (208) 61.3 (60.6) 16:0 (43.9) 18:0 (5.6) 18:1 (40.5) 18:2 (8.6) WCO6 2.10 53.9 (50.7) 11.0 212 (196) 59.9 (62.7) C16:0 (38.8) C18:0 (4.1) C18:1 (47.9) C18:2 (4.2) WCO:CRO =3:1 2.12 69.0 (75.5) 30.1 200 (212) 58.1 (55.1) C16:0 (30.1) C18:0 (3.1) C18:1 (51.9) C18:2 (12.0) C18:3 (2.%) C20:0 (0.2) C22:0 (0.1) WCO:CRO =1:1 2.19 76.8 (90.7) 51.3 188 (203) 58.1 (52.8) C16:0 (21.5) C18:0 (2.1) C18:1 (55.8) C18:2 (14.7) C18:3 (5.1) C20:0 (0.8) C22:0 (0.1) WCO:CRO =1:3 2.24 84.5 (104) 62.4 177 (202) 58.1 (49.9) 14:0 (0.1) 16:0 (14.7) 16:1 (0.7) 18:0 (6.85) 18:1 (40.0) 18:2 (37.0) 18:3 (0.25) 20:0 (0.25) 22:0 (0.15) rapeseed (CRO7) 2.20 118 (123) 71.6 165 (200) 52.8 (45.9) C16:0 (4.1) C18:0 (0.1) C18:1 (63.7) C18:2 (20.2) C18:3 (10.2) C20:0 (1.5) C22:0 (0.2) rapeseed* 4.17-5.12 108 (107) 3.5 203 (200) 48.9 (49.5) C16:0 (7.6) C18:0 (1.3) C18:1 (64.5) C18:2 (23.7) C18:3 (2.4) C20:0 (0.5) Brassica juncea 0.74 109 (110) 178 (185) 52.4 (51.1) C16:0 (2.4) C18:0 (1.1) C18:1 (19.9) C18:2 (19.2) C18:3 (10.9) C20:0 (7.2) C20:1 (1.7) C22:0 (0.9) C22:1 (34.8) 24:0 (1.9) safflower 1.75 139 48.9 170 47.1 n.d. WCO: tobacco2 =1:1 4.34 119 (112) 56.0 191 (203) 48.1 (48.0) C16:0 (22.5) C18:0 (3.2) C18:1 (32.0) C18:2 (42.1) C18:3 (0.2) tobacco2 6.17 141 (151) 33.4 183 (201) 44.4 (39.5) C16:0 (8.7) C18:0 (1.6) C18:1 (12.8) C18:2 (76.0) C18:3 (0.7) C20:0 (0.1) C22:0 (0.1) 1Iodine value; 2Peroxide number; 3Saponification number; 4Cetane number; 5Winterized sunflower oil, 6Waste cooking oil; 7Crude rapeseed oil; * refined, commercial oils acidified with pure oleic acid up to the indicated value. Tab. 3.1. Results of the characterization of the oils. The results of the FFA esterification performed on the different oils are given in Fig. 3.1. Fig. 3.1. Results of the FFA esterification reaction on different oils. The dotted line represents a FFA concentration equal to 0.5%wt, i.e. the limit required by both the European and American directives on BD fuel and to perform the transesterification reaction avoiding excessive soaps formation. The FFA esterification method is able to lower the acidity of most of the oils using the ion exchange resins A46 and D5081 as catalysts in the adopted reaction conditions. High conversion was obtained with A15 at the first use of the catalyst, but then its catalytic activity drastically drops after each cycle. The total loss of activity was estimated to be around 30% within the 5 cycles (results not shown for the sake of brevity). A possible explanation concerning this loss of activity may be related to the adsorption of the H2O yielded by the esterification on the internal active sites, which makes them unavailable for catalysis. When H2O molecules are formed inside the pores, they are unable to give internal retro-diffusion due to their strong interaction with H+ sites and form an aqueous phase inside the pores. The formation of this phase prevents FFA from reaching internal active sites due to repulsive effects. What appears to influence the FFA conversion is the refinement degree of the oil. WCO is in fact harder to process in comparison to refined oils (Bianchi et al., 2010; Boffito et al., 2012c), probably due to its higher viscosity which results in limitations to the mass transfer of the reagents towards the catalyst. Indeed, the required acidity limit is not achieved within 6 hours of reaction. A FFA concentration lower than 0.5%wt is not achieved also in the case of WCO mixture 3:1 with CRO and 1:1 with tobacco oil and in the case of the second stock of tobacco oil (tobacco2). This is attributable to the very low quality of these feedstocks due to the waste nature of the oil itself, in the case of WCO, or to the poor conservation conditions in the case of tobacco oilseed. In this latter case, the low FFA conversion was also ascribed to the presence of phospholipids, responsible for the deactivation of the catalyst. BD yields ranging from 90.0 to 95.0 and from 95.0 to 99.9% were obtained from deacidified raw oils using KOH and NaOCH3 as a catalyst, respectively. In Fig. 3.2, the comparison between A46 and D5081 at different temperatures and in absence of drying pretreatment (wet catalyst) is displayed. As expected, D5081 performs better than A46 in all the adopted conditions. Nevertheless, the maximum conversion within a reaction time of 6 hours is not achieved by any of the catalysts both operating at 318 K and in the absence of drying pretreatment. A more detailed study on the FFA esterification of WCO and its blends with rapeseed oil and gasoline was carried out. In Tab. 3.2 a list of all the experiments performed with WCO is reported together with the FFA conversion achieved in each case, while in Fig. 3.3 the influence of the viscosity of the blends of WCO is shown. Fig. 3.2. Comparison between the catalysts. D5081 and A46 at a) different catalysts amounts and b) temperatures and treatments. The results show that Carberry reactor is unsuitable for FFA esterification since a good contact between reagents and catalyst is not achieved due to its confinement. A15 deactivated very rapidly, while A46 and D5081 maintained their excellent performance during all the cycles of use due to the reasons already highlighted previously. The blends of WCO and CRO show an increase of the reaction rate proportional to the content of the CRO, that is attributable to the decreases viscosity (Fig. 3.3), being all the blend characterized by the same initial acidity. Also the use of diesel as a solvent resulted in a beneficial effect for the FFA esterification reaction, contributing to the higher reaction rate. Feedstock %wtFFAt=0 Reactor Cat. gcat/100 goil gcat/100 g feedstock Number of cat. re-uses FFA conv. (%), 1st use, 6 hr 1 WCO 2.10 Carberry A15 3.3 3.3 6 15.4 2 WCO 2.10 slurry A15 10 10 6 71.7 3 WCO 2.10 Carberry A46 3.3 3.3 6 7.7 4 WCO 2.10 slurry A46 10 10 6 62.0 5 WCO 2.10 slurry D5081 10 10 6 63.7 6 CRO 2.20 slurry A46 10 10 10 95.9 7 CRO 2.20 slurry D5081 10 10 10 93.7 8 WCO 2.10 slurry A46 10 10 0 62.0 9 WCO 75 CRO 25 2.12 7.5 71.3 10 WCO 50 CRO 50 2.19 5.0 79.9 11 WCO 25 CRO 75 2.24 2.5 86.1 12 CRO 2.20 10 95.9 13 WCO 75 DIESEL 25 1.74 7.5 76.8 14 WCO 50 DIESEL 50 1.17 5.0 58.7 15 WCO 25 DIESEL 75 0.65 2.5 40.4 16 WCO 25 DIESEL 75 (higher FFA input) 2.44 2.5 63.5 Tab. 3.2. Experiments performed with waste cooking oil. . Fig. 3.3. FFA conversions and viscosities of the blend of WCO with rapeseed oil. 3.2. Sulphated inorganic oxides as catalysts for the free fatty acid esterification: conventional and ultrasound assisted synthesis Conventional syntheses In Tab. 3.3, the list of all the catalyst synthesized with conventional techniques is reported together with the results of the characterization. Catalyst Composition Prep. method precursors T calc. SSA (m2g-1) Vp (cm3g-1) meq H+g-1 1 SZ1 SO42-/ZrO2 one-pot sol-gel ZTNP1, (NH4)2SO4 893 K O2 107 0.09 0.90 2a SZ2a SO42-/ZrO2 two-pots sol-gel ZTNP, H2SO4 893 K 102 0.10 0.11 2b SZ2b SO42-/ZrO2 two-pots sol-gel ZTNP, H2SO4 653 K 110 0.10 0.12 3 SZ3 SO42-/ZrO2 Physical mixing ZrOCl2.8H2O (NH4)2SO4 873 K 81 0.11 1.3 4 SZ4 Zr(SO4)2/SiO2 Impregnation Zr(SO4)2.4H2O SiO2 873 K 331 0.08 1.4 5 SZ5 Zr(SO4)2/Al2O3 Impregnation Zr(SO4)2.4H2O Al2O3 873 K 151 0.09 0.67 6 ZS Zr(SO4)2.4H2O (commercial) - - - 13 0.12 9.6 7 STTO_0 SO42-/SnO2 Physical mixing + impregnation SnO2 TiO2 P25 H2SO4 773 K 16.8 0.10 3.15 8 STTO_5 SO42-/95%SnO2-5%TiO2 773 K 15.9 0.11 3.43 9 STTO_10 SO42-/ 90%SnO2-10%TiO2 773 K 16.5 0.09 5.07 10 STTO_15 SO42-/ 85%SnO2-15%TiO2 773 K 14.9 0.11 7.13 11 STTO_20 SO42-/ 80%SnO2-20%TiO2 773 K 16.9 0.09 7.33 Tab. 3.3. Sulphated inorganic catalysts synthesized with conventional techniques. The FFA conversions of the sulphated Zr-based systems are provided in Fig. 3.4a and show that Zr-based sulphated systems do not provide a satisfactory performance in the FFA esterification, probably due to their low acid sites concentration related to their high SSA. Even if catalysts such as SZ3 and SZ4 exhibit higher acidity compared to other catalysts, it is essential that this acidity is located mainly on the catalyst surface to be effectively reached by the FFA molecules, as in the case of ZS. In Figure 3.4b, the results of the FFA esterification tests of the sulphated Sn-Ti systems are shown. Other conditions being equal, these catalysts perform better than the sulphated Zr-based systems just described. This is more likely due to the higher acidity along with a lower surface area. With increasing the TiO2 content, the acidity increases as well. This might be ascribable to the charge imbalance resulting from the heteroatoms linkage for the generation of acid centres, (Kataota and Dumesic, 1988). As a consequence, the activity increases with the TiO2 content along with the acidity of the samples. For the sake of clarity, in Fig. 3.4c the FFA esterification conversion is represented as a function of the number of active sites per unit of surface area of the samples. Ultrasound- assisted synthesis In Tab. 3.4, the list of all the catalyst synthesized with conventional techniques is reported together with the results of the characterization. Samples SZ and SZT refer to catalysts obtained with traditional sol-gel method, while samples termed USZT refer to US-obtained sulphated 80%ZrO2-20%TiO2. The name is followed by the US power, by the length of US pulses and by the molar ratio of water over precursors. For example, USZT_40_0.1_30 indicates a sample obtained with 40% of the maximum US power, on for 0.1 seconds (pulse length) and off for 0.9 seconds, using a water/ZTNP+TTIP molar ratio equal to 30. SZT was also calcined at 773 K for 6 hours, employing the same heating rate. This sample is reported as SZT_773_6h in entry 2a. Further details about the preparation can be found in a recent study (Boffito et al., 2012b). Entry Catalyst Acid capacity (meq H+/g) SSA (m2g-1) Vp (cm3g-1) Ave. BJH Dp (nm) Zr:Ti weight ratio S/(Zr+Ti) atomic ratio 1 SZ 0.30 107 0.20 6.0 100 0.090 2 SZT 0.79 152 0.19 5.0 79:21 0.085 2a SZT_773_6h 0.21 131 0.20 5.0 n.d.1 n.d 3 USZT_20_1_30 0.92 41.7 0.12 12.5 80:20 0.095 4 USZT_40_0.1_30 1.03 47.9 0.11 9.5 81:19 0.067 5 USZT_40_0.3_30 1.99 232 0.27 4.5 81:19 0.11 6 USZT_40_0.5_7.5 1.70 210 0.20 5.0 78:22 0.086 7 USZT_40_0.5_15 2.02 220 0.20 5.0 80:20 0.13 8 USZT_40_0.5_30 2.17 153 0.20 5.0 78:22 0.12 9 USZT_40_0.5_60 0.36 28.1 0.10 10 79:21 0.092 10 USZT_40_0.7_30 1.86 151 0.16 5.0 78:22 0.11 11 USZT_40_1_15 3.06 211 0.09 7.0 80:20 0.15 12 USZT_40_1_30 1.56 44.1 0.09 7.0 80:20 0.17 Tab. 3.4. Sulphated inorganic Zr-Ti systems synthesized with ultrasound-assisted sol-gel technique. Some of the results of the characterizations are displayed in Tab. 3.4. The results of the catalytic tests are shown in Fig. 3.5 a, b and c. In Fig. 3.5a and 3.5b the FFA conversions are reported for the samples synthesized using the same or different H2O/precursors ratio, respectively. Fig. 3.5. FFA conversions of sulphated inorganic Zr-Ti systems synthesized with ultrasound-assisted sol-gel for a) the same amount of H2O, b) different amount of H2O used in the sol-gel synthesis, c) in function of the meq of H+/g of catalyst Both the addition of TiO2 and the use of US during the synthesis are able to improve the properties of the catalysts and therefore the catalytic performance in the FFA esterification. The addition of TiO2 is able to increase the Brønsted acidity and, as a consequence, the catalytic activity (compare entries 1 and 2 in Tab. 3.4). The improvement in the properties of the catalysts due the use of US is probably caused by the effects generated by acoustic cavitation. Acoustic cavitation is the growth of bubble nuclei followed by the implosive collapse of bubbles in solution as a consequence of the applied sound field. This collapse generates transient hot-spots with local temperatures and pressures of several thousand K and hundreds of atmospheres, respectively (Sehgal et al., 1979). Very high speed jets (up to 100 m/s) are also formed. As documented by Suslick and Doktycz (Suslick and Doktycz, 1990), in the presence of an extended surface, such as the surface of a catalyst, the formation of the bubbles occurs at the liquid-solid interface and, as a consequence of their implosion, the high speed jets are directed towards the surface. The use of sonication in the synthesis of catalysts can therefore improve the nucleation production rate (i.e. sol-gel reaction production rate) and the production of surface defects and deformations with the formation of brittle powders (Suslick and Doktycz, 1990). For the samples obtained with the US pulses with on/off ratio from 0.3/0.7 on, the conversion does not increase much more compared to the one achieved with the sample obtained via traditional sol-gel synthesis. Their conversion is in fact comparable (see samples USZ_40_0.3_30, USZ_40_0.5_30, USZ_40_0.7_30 and SZT in Fig. 3.5a. The similarity in the catalytic performance of these catalysts may be ascribable to the fact that they are characterized by comparable values of SSA (entries 2, 5, 8, 10 in Tab. 3.4) and, in the case of the catalysts obtained with pulses, also by comparable acidities (entries 5, 8, 10 in Tab. 3.4). A high SSA may in fact be disadvantageous for the catalysis of the reaction here studied for the reasons already highlighted in the previous sections. The best catalytic performance is reached by the sample USZT_40_1_30, i.e. the one obtained using continuous US at higher power. This catalyst results in fact in a doubled catalytic activity with respect to the samples prepared either with the traditional synthesis or with the use of pulsed US. In spite the acidity of this catalyst is lower than that of the samples obtained with the US pulses, it is characterized by a rather low surface area (entry 12 in Tab. 3.4) that can be associated with a localization of the active sites mainly on its outer surface. As evidenced by the FTIR measurements (not reported for the sake of brevity), it is also important to highlight, that only in the case of the USZT_40_1_30 sample, a not negligible number of medium-strong Lewis acid sites is present at the surface, together with a high number of strong Brønsted acid centres. The XRD patterns of the samples were typical of amorphous systems, due to the low calcination temperatures. Samples calcined for a long time (SZT_773_6h) exhibit almost no catalytic activity (results not reported for the sake of brevity). This catalytic behaviour might be ascribable to the loss of part of the sulphates occurred during the calcinations step that result also in a very low acid capacity (see Tab. 3.4). For the sake of clarity, in Fig. 3.5c the FFA conversions as a function of the concentration of the acid sites normalized to the surface area are reported for the most significant samples. For what concerns how the water/precursors ratio affects the catalysts acidity, some general observations can be made: increasing it up to a certain amount increases the H+ concentration (compare entries from 6 to 9 and 11 to 12 in Tab. 3.4) because the rate of the hydrolysis and the number of H2O molecules that can be chemically bounded increases. Nevertheless, increasing the water/precursor ratio over a certain amount (30 for pulsed and 15 for continuous US, entries 8 and 11 in Tab. 3.4, respectively), seems to have a negative effect on the acidity concentration. In fact, the risk of the extraction of acid groups by the excess of water increases as well and the US power density decreases. 3.3 Sonochemically-assisted esterification and transesterification Esterification In Tab. 3.5 a list of the sonochemically-assisted esterification experiments is displayed together with the final acidities achieved after 4 hours of reaction. The reactor used for these experiments, provided with both an US horn (20 kHz) and a MW emitter (2450 MHz) is described elsewhere in detail (Ragaini et al., 2012). Standard calorimetric measurements were carried out to measure the actual emitted power (Suslick and Lorimer, 1989). Considering entries from 1 to 6 (rapeseed oil with high acidity), a final acidity lower than 0.5%wt is achieved within 4 hours operating at the conventional temperature of 336 K with all the methods, while this does not happen operating at lower temperatures. In particular, the lowest acidity is achieved at 336 K with MW. Considering entries from 7 to 12, inherent to the raw tobacco oilseed, final acidities lower than 0.5%wt are achieved only with the use of US. It is remarkable that at the temperature of 293 K the FFA esterification reaction rate results 6X faster than the conventional process at the same temperature. In the case of the rapeseed oil with low acidity (entries from 13 to 20), the use of MW increases the FFA conversion at 293 K and 313 K but not at 336 K. Moreover, the higher the applied power, the higher the FFA conversion. Oil Initial acidity (%wt) Cat. Technique Temp. (K) Emitted power (W) Tthermostat (K) Final acidity (%wt), 4 hr 1 Rapeseed oil (5)* 4.2-5.0 A46 conventional 313 - 315 1.18 2 336 338 0.50 3 ultrasound 313 38.5 293 0.55 4 336 313 0.48 5 microwaves 313 61.4 293 0.69 6 336 313 0.32 7 Tobacco 1.17 A46 conventional 293 - 293 0.97 8 313 315 0.55 9 336 338 0.45 10 ultrasound 293 38.5 277 0.48 11 313 293 0.46 12 336 313 0.30 13 Rapeseed oil (2)* 2.0-2.3 D5081 conventional 293 - 277 0.82 14 313 315 0.44 15 336 338 0.25 16 microwaves 293 31.7 277 0.73 17 313 31.7 293 0.34 18 61.4 293 0.37 19 336 31.7 313 0.29 20 61.4 313 0.25 Tab. 3.5. Sonochemically-assisted esterification experiments. The positive effects of acoustic-cavitation in liquid-solid systems are ascribable to the asymmetric collapse of the bubbles in the vicinity of the solid surface. When a cavitation bubble collapses violently near a solid surface, liquid jets are produced and high-speed jets of liquid are driven into the surface of a particle. These jets and shock waves improve both the liquid–solid and liquid-liquid mass transfer (Mason and Lorimer, 1988). MW is considered as a non-conventional heating system: when MW pass through a material with a dipole moment, the molecules composing the material try to align with the electric field (Mingos et al., 1997). Polar molecules have stronger interactions with the electric field. Polar ends of the molecules tend in fact to align themselves and oscillate in step with the oscillating electric field. Collisions and friction between the moving molecules results in heating (Toukoniitty et al., 2005). The increase of the FFA conversion as the power increases may be attributed to the fact that more power is delivered to the system and, therefore, the enhanced temperature effects caused by electromagnetic irradiation are increased with respect to lower powers. Differently the reason why a too high power was detrimental at the temperature of 336 K could be accounted for by two factors: i) the acoustic cavitation is enhanced at lower temperatures due to the higher amount of gas dissolved; ii) possible generation of too high temperatures inside the reaction medium that could have caused the removal of methanol from the system through constant evaporation or pyrolysis. Transesterification Transesterification experiments were performed on rapeseed oil both in batch and continuous mode. For the batch experiments two kinds of reactors were used: a traditional reaction vessel and a Rosett cell reactor, both with two ultrasound horns with different tip diameters (13 and 20 mm), and operating powers. A Rosett cell is a reactor designed to promote hydrodynamic cavitation through its typical loops placed at the bottom of vessel. Sonicators used in this work were provided by Synetude Company (Chambery, France). In Fig. 3.6, results from the conventional and the US-assisted batch experiments are compared. The US methods allows to attain very high yields in much shorter times than the traditional method and using less reagents (see Tab. 2.3) in just one step. The beneficial effects given by the US are attributable to the generation of acoustic cavitation inside the reaction medium leading to the phenomena already described in the case of esterification reaction. In particular, with the use of the Rosett cell reactor, BD yields of 96.5% (dotted lined) are achieved after 10 minutes of reaction. This is likely due to the combined approach exploiting acoustic cavitation along with hydrodynamic cavitation, which is able to provide a very efficient mixing inside the system. The use of the Rosett cell reactor provided transesterification reaction rates up to 15X faster than the conventional process. Continuous experiments were performed using two tubular reactors with different volumes (0.070 L at 35 KHz and 0.700 L at 20 kHz) and different US powers (19.3 and 68.3 W, respectively). The volume of the treated reagents was varied to obtain the same power density in both the reactors. Results are presented in Fig. 3.7. BD yields higher than 96.5% were obtained in the case of the small reactor within a reaction time of ~5 minutes. It is remarkable that BD yields higher than 90% were obtained using pulsed US (2 seconds on, 2 seconds off) after only 18 seconds, corresponding to just one passage in the reactor. In this case the transesterification reaction rate was 300X faster than the conventional process. The beneficial effects of pulses for the reactivity of the transesterification have been extensively reported (Chand et al., 2010; Kumar et al., 2010). In particular, as reported by Chand, when pulses are adopted, excessive heating of the reaction medium is not promoted, so preventing the loss of the gases dissolved in the system that are necessary for the acoustic cavitation to occur. Moreover, excessive heating during the transesterification reaction might lead to evaporation followed by pyrolysis of methanol and its subsequent removal from the reaction environment. 4. Conclusions As a conclusion to this work, some final remarks can be claimed: Feedstocks with a high potential for biodiesel (BD) production are Brassica juncea oilseed, which can be used as feedstock for BD100, Carthamus tinctorus, tobacco, animal fat and waste cooking oil to be used in BD blends with other oils or in diesel blends. However, blending different oils among them or with diesel already during the free fatty acids (FFA) esterification reaction may increase the reaction rate due to the lowered viscosity. Free fatty acids esterification over acid ion exchange resins in slurry reactors remains the preferred method of oils deacidification due to the optimal contact between the reagents and the catalyst and the good durability over time. The final high BD yields obtained for the oils de-acidified with the pre-esterification method over sulphonic ion exchange resins demonstrate its effectiveness in lowering the acidity and the possibility of obtaining high quality biodiesel from the selected feedstocks. Surface acidity and specific surface area of sulphated inorganic systems can be increased by both adding TiO2 and using ultrasound (US) in precise experimental conditions to assist the sol-gel synthesis of the catalysts. Changing the experimental conditions of US during the sol-gel synthesis makes also possible to tune the properties of the catalysts. In spite of not satisfying FFA conversions were obtained, US-assisted sol-gel synthesis turns out to be an extremely interesting method to obtain catalysts with high acidity and surface area. Both US and microwaves (MW) enhanced the FFA esterification reaction rate at temperatures lower than the one used conventionally (336 K). The positive effects of US are attributable to the phenomena generated inside the reaction medium by the acoustic cavitation, while MW are able to generate temperature effects localized in the proximity of the catalyst surface and to increase MeOH-oil solubility. US-assisted transesterification reaction is much faster than conventional transesterification: BD yields higher than 96.5% were achieved in most of the cases within 10 minutes of reaction, whereas the conventional method requires 150 minutes, besides higher reagents amount and higher temperatures. In particular, BD yields higher than 90% were obtained using a continuous reactor and pulsed US within 18 seconds, corresponding to just one passage in the reactor. In this case the transesterification reaction rate resulted to be 300X faster than the conventional process. Suggestions for the continuations of the work concern the further study of the synthesis of sulphated inorganic systems such as SO42-/ZrO2 or SnO2 or TiO2 with US and MW. Future work should also be devoted to the optimization of the experimental variables related to the use of MW and US to promote both FFA esterification and transesterification reactions. References Barrett E.P., Joyner L.G., Halenda P.P., “The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms”, J. Am. Chem. Soc. 1951, 73, 373. Bianchi C.L., Boffito D.C., Pirola C., Ragaini V., “Low temperature de-acidification process of animal fat as a pre-step to biodiesel production”, Catal. Lett., 2010, 134, 179. Bianchi C.L., Pirola C., Boffito D.C., Di Fronzo A., Carvoli G., Barnabè D., A. Rispoli, R. Bucchi, “Non edible oils: raw materials for sustainable biodiesel”, in Stoytcheva M., Montero G. (Eds.): Biodiesel Feedstocks and Processing Technologies, Intech, 2011, pp. 3-22. Boffito D.C., Pirola C., Galli F., Di Michele A., Bianchi C.L., “Free Fatty Acids Esterification of Waste Cooking Oil and its mixtures with Rapeseed Oil and Diesel”, Fuel, 2012a, accepted on 19th October 2012, DOI: 10.1016/j.fuel.2012.10.069. Boffito D.C., Crocellà V., Pirola C., Neppolian B., Cerrato G., Ashokkumar M., Bianchi C.L., “Ultrasonic enhancement of the acidity, surface area and free fatty acids esterification catalytic activity of sulphated ZrO2-TiO2 systems”, J. Catal., 2012b, http://dx.doi.org/10.1016/j.jcat.2012.09.013 Boffito D.C., Pirola C., Bianchi C.L., “Heterogeneous catalysis for free fatty acids esterification rea.ction as a first step towards biodiesel production”, Chem, Today, 2012c, 30, 14. Brunauer S., Hemmett P., Teller E., “Adsorption of Gases in Multimolecular Layers”, J. Am. Chem. Soc. 1938, 60, 309. López D. E., Suwannakarn K., Bruce D. A., Goodwin JG. “Esterification and transesterification on tungstated zirconia: Effect of calcination temperature”, J Catal 2007, 247, 43. Mason T.J., Lorimer J.P., “Sonochemistry, Theory, Applications and Uses of Ultrasound in Chemistry“, Efford, J. Wiley, New York, 1988. Mingos D.M.P.,Baghurst D.R., “Applications of Microwave Dielectric Heating Effects to Synthetic Problems in Chemistry“, Microwave-Enhanced Chemistry, American Chemical Society,Washington, DC, USA, 1997. Perego C., Ricci, M., “Diesel fuel from biomass”, Catal. Sci. Technol., 2012, 1, 1776. Pirola C., Boffito D.C., Carvoli G., Di Fronzo A., Ragaini V., Bianchi C.L., “Soybean oil deacidification as a first step towards biodiesel production”, in D. Krezhova (Ed.): Recent Trends for Enhancing the Diversity and Quality of Soybean Products, Intech, 2011, pp. 321-44. Pirola C., Bianchi C.L., Boffito D.C., Carvoli G., Ragaini V., “Vegetable oil deacidification by Amberlyst : study of catalyst lifetime and a suitable reactor configuration”, Ind. Eng. Chem. Res., 2010, 49, 4601. Ragaini V., Pirola C., Borrelli S., Ferrari C., Longo I., “Simultaneous ultrasound and microwave new reactor: Detailed description and energetic considerations”, Ultrasonics Sonochemistry 2012, 19, 872 Sehgal C., Steer R.P., Sutherland R.G., Verrall R.E., “Sonoluminescence of argon saturated alkali metal salt solutions as a probe of acoustic cavitation”, J. Chem. Phys., 1979, 70, 2242. Suslick K. S., Doktycz, S. J., "The Effects of Ultrasound on Solids" in Mason, T.J.: Advances in Sonochemistry, JAI Press: New York, 1990, vol.1, pp. 197-230. Toukoniitty B., Mikkola J.P., Murzin D.Yu., Salmi T., “Utilization of electromagnetic and acoustic irradiation in enhancing heterogeneous catalytic reactions”, Appl. Catal. A 2005, 279, 1 Winayanuwattikun P., Kaewpiboon C., Piriyakananon K., Tantong S., Thakernkarnkit W., Chulalaksananukul W. et al. “Potential plant oil feedstock for lipase-catalyzed biodiesel production in Thailand”, Biomass. and Bioen. 2008, 32, 1279.

Nutrients present in digested animal waste can be utilized for algae cultivation under suitable conditions. Algal growth, however, depends on the chemical forms and speciation of these nutrients. In this study a chemical equilibrium model was first used to describe nutrient speciation and predict conditions that enhance the solubility of nutrients in anaerobic digester effluent. Dilution with water and separation of large particulates greatly improved nutrient availability and light penetration - conditions favorable for algal cultivation. Algae growth was tested using three strains - Scenedesmus dimorphous (UTEX # 417), Chlorella vulgaris (UTEX# 265), and an algal isolate (designated as LLAI and later identified to be closely related to Chlorella vulgaris) from the wastewater treatment lagoons in Logan, UT. All tested strains could be adapted to the effluent to enhance the utilization of native nutrients present in both organic and inorganic forms. There was a marked improvement in growth rates (up to 4.8-fold) and biomass production (up to 8.7-fold) of algal cultures after they adapted to the effluent. Also, effluent-adapted strains were able to switch from phototrophy to heterotrophy to prolong the growth when light availability became limited. However, an increase in irradiance levels in light-limited cultures led to resumption of phototrophic growth. It was found that this approach of light supplementation prolonged growth and increased biomass production (up to 2.7-fold) in algal cultures. Of all the strains tested, the isolate from the wastewater treating lagoons grew to highest culture densities and produced the highest concentration of intracellular triacylglycerides (TAG). This culture also grew best in non-sterile, native effluent and could reach biomass concentration of up to 4.5g/L with TAG content of approximately 10% (w/w). Culture densities were lower when this organism was grown in sterilized effluent or in sterile artificial media, suggesting that this organism symbiotically associated with other microbes in digested animal waste. Findings of this research study suggest that microalgae can be grown efficiently on inexpensive natural substrates in non-sterile growth conditions. When commercially implemented, biodiesel production from such systems could be more cost effective and sustainable.

Due to a number of factors, the biodiesel industry in the United States is surging in growth. Traditionally, oil seed crops such as soybean are used as the feedstock to create biodiesel. However, the crop production can no longer safely keep up with the demand for the growing biodiesel industry. Using algae as a feedstock has been considered for a number of years, but it has always had limitations. These limitations were mainly due to the production methods used to grow and harvest the algae, rather than the reaction methods of creating the biodiesel, which are the same as when using traditional crops. Algae is a promising alternative to other crops for a number of reasons: it can be grown on non arable land, is not a food crop, and produces much more oil than other crops. In this project, we propose a novel attached growth method to produce the algae while recycling dairy farm wastewater using the microalga Chlorella sp. The first part of the study provided a feasibility study as the attachment of the alga onto the supporting substrate as well as determining the pretreatment options necessary for the alga to grow on wastewater. The results showed that wastewater filtered through cheesecloth to remove large particles was feasible for production of Chlorella sp, with pure wastewater producing the highest biomass yield. Most importantly, the attached culture system largely exceeded suspended culture systems as a potentially feasible and practical method to produce microalgae. The algae grew quickly and were able to produce more than 3.2 g/m2-day with lipid contents of about 9% dry weight, while treating dairy farm wastewater and removing upwards of 90% of the total phosphorus and 79% of the nitrogen contained within the wastewater. Once the â proof-of-conceptâ work was completed, we investigated the effects of repeat harvests and intervals on the biomass and lipid production of the microalgae. The alga, once established, was harvested every 6, 10, or 15 days, with the remaining algae on the substrate material functioning as inoculums for repeated growth. Using this method, a single alga colony produced biomass and lipids for well over six months time in a laboratory setting. The second part of this study investigated another aspect of biodiesel production from algae. Rather than focus solely on biomass production, we looked into biodiesel creation methods as well. Biodiesel is created through a chemical reaction known as transesterification, alcoholysis, or commonly, methylation, when methanol is the alcohol used. There are several different transesterification methods. By simplifying the reaction conditions and examining the effects in terms of maximum fatty acid methyl esters (FAME) produced, we were able to determine that a direct transesterification with chloroform solvent was more effective than the traditional extraction-transesterification method first popularized by Bligh & Dyer in 1959 and widely used. This synergistic research helps to create a more complete picture of where algal biodiesel research and development is going in the future.
Master of Science

Biodiesel is a clean-burning substitute for petroleum-based diesel produced from virgin or waste vegetable oils and animal fats. One obstacle to the development of biodiesel is its high cost compared to petroleum diesel. Using waste frying oil instead of virgin oil can significantly reduce the high production cost. In our lab, promising preliminary results have indicated that transesterification of waste frying oil catalyzed by sulphuric acid has sufficient commercial feasibility to warrant further investigation. In order to better understand the acid-catalyzed transesterification process and to optimize the process yield, an empirical study of the reaction kinetics was carried out. A mixture design for feed compositions at various temperatures was used to determine their effects on conversion rates and yields. Empirical models were built to describe the relationships of interest. Rate of mixing, feed composition and temperature were chosen as independent factors in this study. Intensity of mixing was found to have no significant effect on the yield over 100 rpm. The methanol to oil ratio and temperature were the most significant factors affecting the yield. Finally, a region of optimum operating conditions was determined from the models. Analytical methods played an important role in our study. The extent of the reaction was followed off-line by gel permeation chromatography (GPC) and compared to results using an off-line infrared sensor based on attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The development, use and evaluation of the off-line method were discussed. The reproducibility of both methods was found to be excellent (≤1%); data obtained from both methods were found to be reliable. Finally, a comparison of the two methods showed good agreement (within 2%) in the monitoring of the transesterification reaction.

Biodiesel is a renewable source of energy typically produced in a chemical process known as transesterification. The process involves the reaction of an alcohol with vegetable oil or animal fat in the presence of a catalyst to yield mono-alkyl esters (biodiesel) and glycerol as a by-product. The biodiesel market is amongst the fastest growing renewable energy markets and there is a genuine interest in its development from industry and academia. However, there are some challenges that are facing biodiesel and hindering its commercialization. The major ones are production cost and quality. The process must be cost-effective whilst producing biodiesel that meets international standards (ASTM D6751 and EN 14214). The main objectives of this project were to investigate the use of a continuous membrane reactor for the production of biodiesel from waste vegetable oil feedstock with high free fatty acid (FFA) content and to investigate the effect of membrane pore size on the separation of soap and triglycerides in the reactor. This was achieved through the construction and operation of a lab scale continuous membrane reactor. The membrane reactor integrates many procedures such as combining the chemical reaction and the membrane-based separation in the same unit. The biodiesel was produced by base-catalyzed transesterification. Two levels of FFA in the waste vegetable oil feedstock were studied, 4.8 and 10 mass%. Ceramic membranes were used, with membrane pore sizes ranging from 1 to 800 nm. It was found that the free glycerol and total glycerol content in the fatty acid methyl ester (FAME or biodiesel) produced were significantly below the maximum limit of the ASTM D6751 standard. There was no trend associating changes in membrane pore size with glycerol concentration. Additionally, it was found that the water content in the FAME produced met the ASTM D6751 standard. Furthermore, the results of the soap analysis indicated that the soap dissolved in the alcohol and passed through the membrane. Thus, soap was not completely retained in the reactor. Therefore, the soap produced as a result of using high FFA feedstock in a base-catalyzed transesterification did not affect the FAME production process and the passage of mono-, di-, and triglycerides through the membrane. The quality of the biodiesel produced in this project met the requirements for the ASTM D6751 standard.

The work reported in this thesis presents an investigation into the various alternative sources of oil for biodiesel production that are considered not to compete with sources of oil for food. Croton megalocarpus seeds, an oil seed from a tree commonly found in eastern Africa has been selected for this study. Currently, Croton megalocarpus tree is used for timber and building poles and as barriers among farmlands. The tree is large and grows to about 30 to 40m high and the seeds produced oil (30 - 35%) but are not consumed because of its cathartic property. The tree grows on marginal lands where no agronomic practices are required. It also serves as a mulching tree that helps to restore the forest vegetation. Field work was undertaken to Kenya for this study. The Croton megalocarpus seeds were studied for their physical and mechanical properties. The size, shape, surface area, angle of repose, coefficient of friction, moisture content and the compression behaviour of the seeds were studied and reported on. The oil from Croton seeds was studied and reported upon for its properties and constituents such as density, gross calorific value, ash content, carbon, hydrogen and oxygen at the fuel oil bunker and analysis services (FOBAS), Llyods Register London. The oil was converted to biodiesel following the method outlined in BS 14105 method. The Croton oil was found to have a calorific value of 40,280kJlkg. The biodiesel properties were analysed on a GC machine to find out the compositions of its methyl ester. The biodiesel was then tested according to BS8186-C on a Perkins D3142, 3 cylinder, 4 stroke, DI marine engine to determine the performance and exhaust emissions as compared to a no 2 diesel. The performance of the biodiesel has been found to be comparable to the normal hydrocarbon diesel and the exhaust emissions has shown a significant drop in the regulated exhaust gases (CO, PM, Smoke, HC), with a slight increment in the exhaust of NO x at some speed and load range. The results of the research presented the Croton properties that lead to a conclusion that Croton oil is a viable and alternative source of biodiesel. Recommendations were made as to ways of improving the oil yields and better agronomic practices to shorten the maturity period of the tree.

Doutoramento em Engenharia Química
Os biocombustíveis têm estado na linha da frente das políticas energéticas mundiais visto que as suas vantagens conseguem colmatar as incertezas e resolver alguns dos problemas associados aos combustíveis fósseis. O biodiesel tem provado ser um combustível muito fiável, alternativo ao petrodiesel. É uma mistura de ésteres alquílicos produzidos a partir de óleos vegetais e gorduras animais através de uma reacção de transesterificação. Como combustível, o biodiesel é economicamente viável, socialmente responsável, tecnicamente compatível e ambientalmente amigável. O principal desafio associado ao seu desenvolvimento tem a ver com a escolha de matéria-prima para a sua produção. Nos países do terceiro mundo, óleos alimentares são mais importantes para alimentar pessoas do que fazer funcionar carros. Esta tese tem como objectivos produzir/processar biodiesel a partir de recursos endógenos de Timor-Leste e medir/prever as propriedades termodinâmicas do biodiesel, a partir das dos esteres alquílicos. A síntese do biodiesel a partir dos óleos de Aleurites moluccana, Jatropha curcas e borras de café foram aqui estudados. As propriedades termodinâmicas como densidade, viscosidade, tensão superficial, volatilidade e velocidade do som também foram medidas e estimadas usando modelos preditivos disponíveis na literatura, incluindo as equações de estado CPA e soft-SAFT. Timor-Leste é um país muito rico em recursos naturais, mas a maioria da população ainda vive na pobreza e na privação de acesso a serviços básicos e condições de vida decentes. A exploração de petróleo e gás no mar de Timor tem sido controlado pelo Fundo Petrolífero. O país ainda carece de electricidade e combustíveis que são cruciais para materializar as políticas de redução da pobreza. Como solução, o governo timorense criou recentemente o Plano Estratégico de Desenvolvimento a 20 anos cujas prioridades incluem trazer o desenvolvimento do petróleo do mar para a costa sul de Timor-Leste e desenvolver as energias renováveis. É neste último contexto que o biodiesel se insere. O seu desenvolvimento no país poderá ser uma solução para o fornecimento de electricidade, a criação de empregos e sobretudo o combate contra a pobreza e a privação. Para ser usado como combustível, no entanto, o biodiesel deve possuir propriedades termodinâmicas coerentes com as especificadas nas normas da ASTM D6751 (nos Estados Unidos) ou EN 14214 (na Europa) para garantir uma adequada ignição, atomização e combustão do biodiesel no motor.
The biofuels have been at the forefront of global energy policies as their advantages can overcome the uncertainties of fossil fuels. Biodiesel has proven to be a very reliable fuel alternative to petrodiesel. It is a mixture of fatty acid alkyl esters obtained by the transesterification of vegetable oils and animal fat. As fuel, biodiesel is economically viable, socially responsible, technically compatible and environmentally friendly. The main challenge associated to its development concerns the choice of raw materials for its production. In third world countries, edible oils are more important for feeding people than for running cars. This thesis aims to produce / process biodiesel from resources endogenous of Timor-Leste and to measure/predict the thermodynamic properties of biodiesel, from those of alkyl esters. The synthesis of biodiesel from oils of Aleurites moluccana, Jatropha curcas and coffee waste were here studied. The thermodynamic properties such as density, viscosity, surface tension, volatility and speed of sound were also measured and estimated using predictive models available in the literature including some equations of state like CPA and soft-SAFT. Timor Leste is a country rich in natural resources, but the majority of the population still lives in poverty and deprivation of access to basic services and decent living conditions. The exploitation of oil and gas in the Timor Sea has filled only the Oil Fund. The country still lacks electricity and fuels that are crucial to materialize policies for poverty reduction. As a solution, the Timorese government has recently established the Strategic Development Plan of 20 years whose priorities include bringing the development of oil from the sea to the south coast of Timor-Leste and developing renewable energy sources. It is in this latter context that biodiesel should be considered. Its development in the country will be contextually an appropriate solution for electricity supply, job creation and especially combat against poverty and deprivation. To be used as fuel, however, biodiesel must possess thermodynamic properties consistent with those specified in the standards of ASTM D6751 (in USA) or EN 14214 (in Europe) to ensure proper ignition, atomization and combustion in diesel engines.

Increasing energy consumption in Australian transport sector, rapidly depleting amount of Australian oil reserves, and the environmental concerns that arise from the associated greenhouse gas emissions produced by the combustion of large amount of fossil fuels during transport activities have increased the interest in using renewable transport fuels, especially ethanol and biodiesel, as replacements for petrol and diesel fuels, respectively, in the transport sector.In Western Australia, there is a potential for replacing diesel fuel consumed in its transport sector by biodiesel produced from rapeseed (canola) grown as one of the break crops between cereal crops. Apart from the availability of raw material, sustainable biodiesel production from rapeseed needs to be analysed from, among other factors, its energy efficiency, which can be determined from the energy ratio of the overall biodiesel production process, defined as the ratio of energy output from biodiesel to the total primary energy consumed during rapeseed growing and processing into biodiesel.In this study, the energy ratio of biodiesel production from rapeseed in Western Australia is evaluated through an energy balance analysis, considering typical Western Australian rapeseed growing practices and rapeseed processing parameters. The energy ratio is then used to evaluate the land, water, and labour requirements of a large scale biodiesel production to analyse its feasibility as a replacement for fossil diesel fuel consumption in Western Australian transport sector. The energy ratio and feasibility of the biodiesel production process are then compared to those of ethanol production from mallee in Western Australia since both biofuels are produced as alternative transport fuels and an assessment is therefore needed to decide which fuel is more feasible to produce, considering the competition for limited resources, e.g. arable land, during their production.Without by-products utilisation, the energy ratio of biodiesel production from rapeseed is found to be less than 1, indicating a negative energy return. The most significant improvement to the energy ratio is achieved when all by-products are utilised, resulting in an energy ratio of 1.70.A feasibility analysis using the net energy approach with an energy ratio of 1.70 shows that the land and labour requirements of a large scale biodiesel production are the major constraints to its realisation as an alternative to diesel fuel in Western Australian transport sector. Replacement of a significant fraction of diesel fuel consumption in the transport sector would cause severe competition for arable land with production of other crops. The net biodiesel production rate is also lower than that required to maintain the current transport activities that are supported by diesel fuel produced by Western Australian energy sector.Feasibility analysis of large scale ethanol production shows, on the other hand, that there is potential to replace approximately 15% of the total petrol fuel consumption in Western Australian transport sector with ethanol produced from mallee grown in Western Australian wheatbelt to tackle dryland salinity problem. The net ethanol production rate would also be sufficient to maintain the current transport activities that are supported by petrol fuel produced by Western Australian energy sector. The feasibility of the large scale ethanol production is, however, dependent on the availability of sufficient water, and hence rainfall, to maintain a consistent mallee yield per hectare of agricultural area.The results of energy balance and feasibility analyses in this study imply that wide implementation of rapeseed-based biodiesel in Western Australia is unsustainable. Possible future implementation should be directed at smaller and more specific targets and should be supported by development of key strategies in both rapeseed growing and rapeseed processing stages aimed at increasing rapeseed yield and reducing main energy input contributors to improve the energy ratio and productivity of the whole production process. The results also show that ethanol production from mallee grown in Western Australian wheatbelt to tackle dryland salinity problem provides an option for a large scale biofuel production to play significant role in future energy security in Western Australian transport sector.

Based on results of its Aquatic Species Program (1978-1996), which sought to develop algae-to-liquid fuel technology, the U.S. Department of Energy has suggested that algal wastewater treatment may be incorporated into biodiesel production schemes to reduce the operating costs of both processes. the purpose of the current research was to evaluate the triglycerides produced by wastewater-grown algae for their suitability as a fuel feedstock and to investigate the effectiveness of several solvent mixtures and extraction procedures at recovering lipids from fresh algae. The research involved two separate experiments. The first determined the quantity and quality of lipids produced over the lifetime of a batch culture of algae grown in a small outdoor high-rate pond. Transesterification of the algal triglycerides yielded mostly saturated and monounsaturated 16 and 18-carbon fatty acid methyl esters, together comprising approximately 8 to 30% of the biomass in the pond. The average triglyceride production rate during the grwoth phase of the culture was 0.97 grams per square meter of pond surface per day. The second experiment compared several industrially practicable extraction procedures to the Bligh and Dyer laboratory extraction method. The Bligh and Dyer laboratory extraction procedure provides excellent lipid recovery efficiency, but several factors limit its potential on an industrial scale. The Bligh and Dyer method requires a larger volume of solvents than other methods, uses the probable carcinogenic chemical chloroform, and involves a complex series of steps that are difficult to automate. A simple, low-energy extraction process using relatively non-toxic solvents was found to have an extraction efficiency comparable to that of the laboratory method.

Actualment la producció de biodièsel està limitada a causa de falta de les matèries primeres econòmicament accesibles i relativament económiques. Fangs municipals generats a les EDAR són una matèria primera prometedora de lípids no comestible que pot emplear-se per a la producció de biodièsel rendible.. Entre els quatre tipus de fangs generats en EDARs, el fang primari és el més beneficiós. No obstant això, la necessitat d'eliminar l'alt contingut d'aigua dels fangs, abans de l'extracció dels lípids, és una limitació principal per la ampliació de procés. Per tant, aquest estudi principalment investiga mètodes alternatius, extracció directa de lípids de fang líquid per tal d'eliminar el costós procés d'assecament de fang. La clàssica extracció líquida-líquida directa dels lípids de fang líquid utilitzant hexà és factible després de l'acidificació dels fangs. L'optimització, ampliació i anàlisi econòmica del procés indiquen que la producció de biodièsel a través de l'extracció líquida-líquida directa dels lípids de fang primari és econòmicament viable i més rentable que la de fang sec. Encara que la tecnologia actualment disponible (extracció líquida-líquida usant hexà) permet una fàcil extracció de lípids a partir de fangs d'aigües residuals, l'ús de líquids iònics com un dissolvent alternatiu verd també ha estat investigat amb la finalitat de millorar l'impacte ambiental del procés. Els líquids iònics no volàtils també mostren un alt potencial per a l'extracció directa de lípids de fang primari, donant resultats comparables als del mètode clàssic. A més, el líquid iònic específic a base de fosfoni és molt prometedor per la seva capacitat per recuperar la cellulosa i proteïnes, juntament amb els lípids en un sol pas, donant un altre avantatge sobre els dissolvents orgànics. Finalment, la síntesi de biodièsel a partir de lípids extrets es va estudiar utilitzant líquids iònics àcids de Brønsted com un catalitzador alternatiu, capaç de superar els problemes relacionats amb els catalitzadors convencionals. Els líquids iònics àcids de Brønsted amb un grup àcid sulfònic d'alcà mostren un bon rendiment catalític per a la conversió dels lípids de fang en biodièsel.
Actualmente la producción de biodiesel está limitada debido a falta de las materias primas accesibles y relativamente económicas. Fangos municipales generados en las EDAR son una materia prima prometedora de lípidos no comestible que pueden utilizarse en la producción de biodiesel. Entre los cuatro tipos de fangos generados en EDARs, el lodo primario es el más beneficioso. Sin embargo, la necesidad de eliminar el alto contenido de agua de los fangos, antes de la extracción de los lípidos, es una limitación principal para la ampliación del proceso. Por lo tanto, este estudio principalmente investiga métodos alternativos, extracción directa de lípidos de fango líquido con el fin de eliminar el costoso proceso de secado de fango. La clásica extracción líquida-líquida directa de los lípidos de fango líquido utilizando hexano es factible tras la acidificación anterior de fangos. La optimización, ampliación y análisis económico del proceso indican que la producción de biodiesel a través de la extracción líquida-líquida directa de los lípidos de fango primario es económicamente viable y más rentable que la de fango seco. Aunque la tecnología actualmente disponible (extracción líquida-líquida usando hexano) permite una fácil extracción de lípidos a partir de fangos de aguas residuales, el uso de líquidos iónicos como disolvente alternativo verde también ha sido investigado con el fin de mejorar el impacto ambiental del proceso. Los líquidos iónicos no volátiles también muestran un alto potencial para la extracción directa de lípidos de fango primario, dando resultados comparables a los del método clásico. Además, el líquido iónico específico a base de fosfonio es muy prometedor debido a su capacidad para recuperar la celulosa y proteínas, junto con los lípidos en un solo paso, dando otra ventaja sobre los disolventes orgánicos. Finalmente, la síntesis de biodiesel a partir de lípidos extraídos se estudió usando líquidos iónicos ácidos de Brønsted como catalizador alternativo, capaz de superar los problemas relacionados con los catalizadores convencionales. Los líquidos iónicos ácidos de Brønsted con un grupo ácido sulfónico de alcano muestran un buen rendimiento catalítico para la conversión de los lípidos de fango en biodiesel.
Production of biodiesel is currently limited due to lack of economically beneficial feedstocks. Municipal sludge generated in WWTPs is a promising non-edible lipid feedstock which can make the biodiesel production profitable. Among the four types of sludge generated in WWTPs, the primary sludge is the most beneficial. However, the need to eliminate the high water content from sludge, before lipid extraction, is a main limitation for scaling up. Therefore, this study primarily investigates alternative methods, direct extractions of lipids from liquid sludge in order to eliminate the expensive process of sludge drying. The classical direct liquid-liquid extraction of lipids from liquid sludge using hexane is feasible after previous sludge acidification .The optimisation, scale-up and economic analysis of the process indicate that the biodiesel production via direct liquid-liquid extraction of lipids from primary sludge is economically feasible and more cost-effective than from dry sludge. Although the technology currently available (liquid-liquid extraction using hexane) allows easy extraction of lipids from sewage sludge, the use of ionic liquids as a green alternative solvent is also investigated in order to improve the environmental impact of the process. The non-volatile ionic liquids also show a high potential for direct lipid extraction from liquid primary sludge, giving results comparable to the classical method. Furthermore, the specific phosphonium-based ionic liquid is very promising due to its ability to recover the cellulose and proteins, together with lipids in one step, giving another advantage over the organic solvents. Finally, the synthesis of biodiesel from extracted lipids is studied using Brønsted acidic ionic liquids as an alternative catalyst, capable to overcome the problems related to conventional catalysts. The Brønsted acidic ionic liquids with an alkane sulfonic acid group show a good catalytic performance for the conversion of sludge lipids into biodiesel.

Damage to the environment as a consequence of exploration, production, imminent depletion, use of fossil fuels and concerns over climate change (increasing lifecycle greenhouse gas emissions), has increased the need for a more eco-friendly, renewable and sustainable source of energy. The level of biodiesel production has been increasing over the last twenty years, reflecting a rapid rise in demand due to its availability, renewability, lower gas emissions, non-toxicity, and its biodegradability. The impact of CO2 emissions on climate change, worldwide industrialisation, countries not having oilfields and need for a strategic and alternative source of energy have also driven an ever increasing demand. Biodiesel is mainly produced in industry by the transesterification process of triglycerides with low molecular weight alcohols using homogenous acid or base catalysts. However, the biodiesel industry faces some significant challenges; (i) high cost of biodiesel feedstock and (ii) the cost of biodiesel processing, including separation, purification and the neutralisation of by-products. These issues can be resolved with catalysts that are highly tolerant to moisture and free fatty acid (FFA) in feedstock oils. Solid acid catalysts have shown promise as catalysts in the simultaneous esterification and transesterification to overcome these issues. Here, lab-scale biodiesel production from simultaneous esterification and transesterification of used cooking oil (UCO) over different developed novel solid acid catalysts has been investigated. The synthesised catalysts, including TiO2/PrSO3H, Ti(SO4)O and SO_4^(2-)/Fe-Al-TiO2, were characterised via XRD, SEM, TEM, TEM-EDS, EDS-mapping, FT-IR, DRIFT-pyridine, TPD-MS with n-propylamine, TGA/FT-IR, CHNS analysis, DSC, TGA, N2 porosimetry, VSM and XPS. The effect of different process parameters on the fatty acid methyl ester (FAME) yield over different catalysts was also studied, including the effect of reaction temperature, mole ratio of methanol to UCO, time of esterification/transesterification, and amount of catalyst to UCO loading in order to achieve the optimum process conditions to obtain the highest FAME yield. Furthermore, a significant aim was to design a highly active, low cost, stable, easy recoverable, FFA tolerant and highly re-usable solid acid catalyst for biodiesel fuel production. It was found that SO_4^(2-)/Fe-Al-TiO2 performs well under optimum conditions of 2.5 h of reaction time, 3 wt% of synthesised magnetic catalyst to UCO ratio, 10:1 methanol to UCO mole ratio and 90 oC reaction temperature for simulations esterification and transesterification processes. A massive improvement in catalytic stability, easy recovery (using external magnetic field), high tolerance to FFA and water have been achieved via the introduction of alumina and iron oxides to the catalyst support. The synthesised biodiesels from UCO over different solid acid catalyst processes were analysed in accordance to ASTM D6475 and EN14214 standard methods to determine characteristic fuel properties such as kinematic viscosity, density, flash point, FAME content, LAME content, and acid number.

Biodiesel is a recommended petroleum-based diesel substitute mainly because it is environmentally friendly and is a renewable, domestic resource. However, compared to petroleum-based diesel, biodiesel has a higher cost, which is the major obstacle to its commercialization. In this thesis, four different continuous alkali- and acid-catalyzed processes to produce biodiesel from virgin vegetable oil and waste cooking oil were designed and simulated. Process flowsheets, along with detailed operating conditions and equipment designs for each process were created. Technical assessment of these processes showed that the alkali-catalyzed process using virgin oil required the least amount of process equipment and no significant requirement for special materials of construction but had the highest raw material cost. The acid-catalyzed process using waste cooking oil proved to be technically feasible with a significantly lower raw material cost but required forty percent of the process equipment to be constructed from stainless steel. An economic assessment was also performed based on the results of process simulations. The alkali-catalyzed process using virgin vegetable oil was found to have the lowest fixed capital cost. However, in terms of total manufacturing cost, aftertax rate of return and break-even price of biodiesel, the acid-catalyzed process using waste cooking oil had the lowest operating cost, the best aftertax rate of return (i.e., 10%) and the lowest break-even price (i.e., $590/tonne). In summary, the acid-catalyzed process to produce biodiesel from waste cooking oil is technically feasible and economically attractive. Results from the sensitivity analyses of the various processes indicated that plant capacity, the price of feedstock oil and biodiesel price were the factors that most significantly affected the economic feasibility of biodiesel production.

There is an increasing need for renewable energy sources to replace fossils fuels which accumulate harmful byproducts in the environment. Biodiesel emits less gaseous pollutants than diesel. There are various sources for biodiesel but they are unable to meet the existing demands for fuel. Microalgae are a promising source for biodiesel because of its relatively faster growth rate, availability, and lipid content. Microalgae (JC and BT) growing in local water bodies were collected, selected on section media containing antibiotics, and used for characterizations. Experiments were conducted to study and evaluate the optimum growing conditions. Results show that both JC and BT attain maximum growth with shaking and additional aeration compared to control microalgae Dunaliella salina, Nannochlorposis oculata which do not require additional aeration for optimal growth. Lipid extraction results suggest that JC (9.7%) and BT (4.1%) have slightly higher lipid content compared to control algae e.g. Chlamydomonas reinhardtii (3.1%).

Growing concerns regarding the impact of fossil fuel use upon the environment and the cost of production have led to a growth in the interest of obtaining energy from biomass. 1st and 2nd generation biomass types, however, are often criticised for their high energy requirements and environmental impacts. Algal biomass is considered a 3rd generation biomass which does not require arable land for cultivation, typically has a high productivity and can be converted to a wide variety of energy carriers. Despite research on the concept of producing energy from algal biomass dating back to the 1960s there has been limited commercial development and the environmental advantages are still in doubt. This thesis investigated the potential of algal biomass as a source of bioenergy feedstock by considering the cultivation and processing of localised species of algae and applying life cycle assessment (LCA) methodology to algal biofuel production systems. Experiments were conducted to examine the productivity of a wild algal species in wastewater and the potential recoverable bioenergy yields. The LCA studies drew together data from external studies, commercial databases, industrial reports and experimental work to assess the environmental impacts and the energy balance for each system considered. The thesis investigated the generation of biofuel from both freshwater algal biomass and marine algal biomass. For both cases, the current state of research was examined and the gaps determined. Existing studies suggest the high intensity of microalgal biomass production (fertiliser requirements, high energy harvesting) greatly reduces the overall sustainability. Part of this thesis therefore investigated the possibility of a low input system of microalgal cultivation. A recommended approach was suggested using local species cultivated in wastewater as the nutrient source and a conversion strategy based on the characteristics of the dominant species. The practicality and effectiveness of cultivating and processing locally grown algal biomass under low input conditions was determined by experiments that were conducted in the laboratory. Algal biomass was collected locally and cultivated in the laboratory using agricultural effluent as the nutrient source. The productivity of the algae was monitored alongside the uptake of nutrients. The effluent provided a good media for the cultivation of the wild algae and the nitrogen and phosphorous loading of the effluent was reduced by as much as 98% for NH4+ and 90% for PO4³-. The algal biomass was also tested for its potential as a feedstock for bioethanol production as well as biochar alongside pyrolysis oils and gases. Compared to alternative biomass types tested, the algal biomass appeared to be a good candidate for bioethanol production providing a 38% recovery of bioethanol. The biomass appeared a less favourable substrate for energy recovery from pyrolysis but this process could be considered for carbon biofixation. The sustainability of incorporating microalgal cultivation in wastewater treatment was tested by conducting a life cycle assessment of a large scale system. The life cycle assessment used Haifa wastewater treatment plant in Israel as a case study. The study compared algal cultivation with energy recovery to conventional nutrient removal (A2O process) for enhanced nutrient removal within the wastewater treatment plant. It was found that the use of algal ponds for nutrient removal compared favourably to conventional treatment under specific conditions. These conditions were: the algal biomass is converted to both biodiesel and biogas and the algal biomass is converted to biodiesel, bioethanol and biogas. In these cases the energy balance was greater and the global warming potential and eutrophication potential were less. The conventional nutrient removal was, however, found to be the better method in terms of the acidification potential. Despite being the favourable method of nutrient removal the cultivation and processing of algae relies upon several key assumptions: high year round growth of algae, no contamination and access to a high land area for the cultivation ponds. The sustainability of recovering bioenergy from the cultivation of macroalgae was also tested. A life cycle assessment was conducted investigating the energy return on investment and six environmental impacts for three cultivation methods and three process streams to convert the biomass to bioenergy. Cultivation and processing in Chile was used as a case study due to the depth of knowledge and availability of data. The cultivation scenarios were: bottom cultivation of Gracilaria chilensis, the long line cultivation of Gracilaria chilensis and the long line cultivation of Macrocystis pyrifera. The processing streams were: bioethanol, biogas and both bioethanol and biogas. Most of the data used in the life cycle assessment was obtained from studies conducted in Chile and from communication with local fisherman. It was found that the bottom cultivation of Gracilaria chilensis and conversion to bioethanol and biogas produced the best energy return on investment (2.95) and was most beneficial in terms of the environmental impacts considered. Alternative circumstances were also considered which included new research (untested on a large scale) related to the value used for productivity and conversion of the biomass. This analysis indicated that an EROI of 10.3 could be achieved for the long-line cultivation of Macrocystis pyrifera and conversion to bioethanol and biogas alongside very limited environmental impacts. This result relies, however, upon favourable assumptions that have not yet been proven on a large scale. The work conducted in this thesis highlights the potential of recovering energy from algal biomass. The experimental work and life cycle analysis of freshwater algal cultivation demonstrates the importance of using wastewater treatment as added value to the system. Maximising energy recovery by using a combination of conversion techniques was also shown to be key in providing the most sustainable solution. The sustainability of energy produced from macroalgae was established as being preferable to several conventional energy sources. Innovative methods to improve the system were also shown to greatly enhance the concept.