Submitted in the fulfillment of the requirements for the degree of Master of Technology, Durban University of Technology, Durban, South Africa, 2011. / The main objective of this study was to evaluate the feasibility of conversion of crude tall oil and tall oil fatty acids into biodiesel. During the Kraft pulping process, Crude Tall Oil originates as tall oil soap, which is separated from recovered black liquor. The soap is then converted to Crude Tall Oil by acidulation with sulphuric acid. The Crude Tall Oil is then fractionated by distillation to produce tall oil fatty acids (TOFA), rosin and pitch. There were a number of conversional methods that were considered but proved to be inappropriate. A base-catalyzed method was inappropriate with due to the high free fatty acid content on the feedstock, and the acid-base catalyzed method was inappropriate due to the long reaction times and large excess of methanol required. An enzyme based conversion method was also found to be inappropriate because of the high price attached to the purchasing of the enzymes and the stability of the enzyme. A procedure of choice was the supercritical methanol treatment, due to the fact that it requires no separate catalyst. A procedure was developed for both the feedstocks (i.e. crude tall oil and tall oil fatty acids) using the supercritical methanol treatment. In supercritical methanol treatment, feedstock and methanol were charged to a reactor and were subjected to temperatures and pressures beyond the critical point of methanol (Tc = 240 °C, Pc = 35 bar). The maximum biodiesel yield obtained from Crude tall oil was 66% and was 81% for the tall oil fatty acids that was produced in a single stage process. The temperature and methanol to feedstock ratio effects was also found to yield a maximum biodiesel yield at 325°C and 40:1 respectively. A 20 minutes reaction time was found to be appropriate for the maximum yield of biodiesel. The final biodiesel produced was also evaluated against a commercial biodiesel product and its parameters measured. The biodiesel resulting from the tall oil fatty acid yielded parameters that were acceptable according to ASTM D6751 specifications for biodiesel. The biodiesel produced from the crude tall oil did not meet the ASTM D6751 specification, and this was mostly attributed to the presence of unsaponifiables which hindered the conversion of oil into biodiesel. / M

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering September 2017 / Owing to the ongoing advancement in technology, escalating population sizes and urbanization rate, fossil fuels (coal, petroleum oil and natural gas) remain attractive as an energy source to run most of the daily operations. Consequent to heavy consumption of fossil fuels, the world faces detrimental challenges such as future energy security and environmental concerns. Combustion of fossil fuels results in emission of greenhouse gases such as CO2 and SO2 thereby contributing to global warming and acid rain problems. These alarming challenges drive the need for exploration of alternative energy sources to reduce dependence on fossil fuels. Presented in this dissertation is a study of biodiesel, a biodegradable, non-toxic and environmentally benign energy source as an alternative to petroleum-based fuels. Chemically known as fatty acid alkyl ester (FAAE), biodiesel is commonly produced from vegetable oils or animal fats in addition to methanol by a catalysed transesterification reaction. Currently, biodiesel is more expensive than petroleum diesel due to high operation costs incurred during the production process. Despite the high prices, biodiesel production continues to grow on an industrial scale across the world as supported by policy measures and biofuel targets. Researchers have identified two main factors that contribute to high costs of biodiesel production; 1) type of feedstock and 2) type of catalyst used in the production process. Conventional methods of production use edible oils as feedstock. This becomes unjustified due to the potential price hikes in the food market owing to the prospective competition between fuel and food industries. As a result, numerous researchers reported on the use of cheap and non- edible feedstock oils such as waste cooking oil and animal fat. However, the challenge with the use of non-edible oils is their high content of free fatty acids (FFA) which is unattractive for a smooth transesterification process, more especially when homogeneous base catalysts are used. Homogeneous base catalysts are widely used in current industrial biodiesel production methods because they yield faster transesterification processes due to increased reaction rates. However, these types of catalysts are much sensitive to FFA, so when high FFA content feedstock is used, a saponification reaction occurs which consequently reduces the yield of biodiesel. An additional process unit is required to reduce the FFA content via esterification process prior to the main transesterification reaction. Furthermore, since the reaction mixture is homogeneously combined with the product, an additional process unit for product separation is required to recover the resulting biodiesel from the mixture, translating into additional production costs. Researchers are currently exploring the use of heterogeneous catalysts, which tend to avoid the saponification reaction and reduce the need for an esterification reaction used as oil pre-treatment step to reduce FFA content. This dissertation is therefore dedicated to attaining a economic and environmentally attractive process for biodiesel production using cheap non-edible beef tallow oil (BTO) and a heterogeneous hydroxy sodalite (H-SOD) catalyst. Some industrial operations such as zeolite manufacturing processes produce a low grade H-SOD as by products, which is in turn disposed as chemical waste and therefore induces ground water contamination concerns. Exploration on the use of H-SOD as catalyst can largely contribute to the environmental protective measures as a waste management process among other benefits. The use of H-SOD is extensively reported in current research development on membrane separation; limited research reports on the use of H-SOD material to catalyse chemical processes are present in literature. For the first time in open literature, H-SOD is reported as the solid catalyst for biodiesel production in this dissertation. The investigative study commenced with a preliminary study to gauge the feasibility of using H-SOD as a catalyst where a batch transesterification of waste cooking oil (WCO) was studied. The reaction was conducted at 60 ᵒC for 12 h at a methanol-to-WCO ratio of 7.5:1 using 3 wt. % H-SOD catalyst with a particle size of just below 300 Å, the stirring intensity was kept at 1000 rpm to ensure uniform mixing throughout the reaction. The product obtained after the reaction was analysed using a pre-calibrated Chromatography-Mass Spectrometer (GC-MS) described in Chapter 5, and the results demonstrated the possibility of catalysing a transesterification reaction using solid H-SOD. Under the same reaction conditions, the study was then extended to an investigation on the use of H-SOD to catalyze transesterification of BTO (4.53 % FFA) to FAME. The results showed that FAME was produced, at a yield of 39.6% and a conversion of 68.4%. Seeing that the yield and conversion obtained is relatively small compared to literature findings, the effect of some process conditions on the conversion and biodiesel yield were studied. The transesterification reaction was conducted with variations in the mixing intensity (700 – 1250 rpm), catalyst particle size (200 – 300 Å), reaction time (6 – 24 h) and reaction temperature (40-60 °C). The maximum performance of H-SOD catalyst for a transesterification of BTO was achieved with a conversion of 78.3% and biodiesel yield of 62.9% obtained at optimum conditions: a stirrer speed of 1000 rpm, with the smallest catalyst particle size of 200 Å at maximum temperature of 60 °C and 24 h reaction time. The values of activation energy, reaction constants and frequency factor obtained from the kinetic study were 0.0011 min-1, 5.52 x108 min-1 and 79.20 kJ/mol, respectively, and are within the range of the results reported in literature. As a result, solid H-SOD is recommended as a catalyst for the batch transesterification of BTO in a biodiesel production process. / MT2018

Thesis submitted in partial fulfilment of the requirements for the degree of Master of Science in Engineering at the School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand Johannesburg, South Africa October, 2017 / The significant increase in the primary energy demand and the effort to reduce harmful emissions related to the greenhouse gases enhanced the search for alternative energy. Production and modelling processes of biofuel from non-edible oil sources assist in the process development of an environmentally friendly fuel such as biodiesel. This work focused on the kinetic modelling of biodiesel synthesised from non-edible oils. Two types of non-edible oils (Jatropha curcas seed oil and Tobacco seed oil) were used in this study including the development of the kinetic behaviour of the transesterification reaction. A linear polynomial model was generated from experimental data found in literature in order to study the influence of operating parameters during biodiesel production. It was found that the temperature improves the yield of biodiesel; this is attributed to the fact that temperature affects the reaction rate constants; and the higher the reaction rate, the lower the activation energy required for a reaction to occur. The optimum conditions for the transesterification of Jatropha curcas seed oil are a temperature of 55 0C, methanol to oil ratio of 6:1, catalyst concentration of 1.2% KOH (by volume of oil), and agitation speed range of 0-250 rpm. Results from both the homogeneous and heterogeneous reactions of Jatropha curcas oil and tobacco seed oil were used to verify the theoretical kinetic and empirical models. It was found that both models describe the kinetic behaviour of transesterification with minor deviations in the estimated parameters. However, the use of empirical model in determining the reaction order, as opposed to the theoretical assumption, gave a second order with respect to oil triglycerides at a temperature of 60 0C. The theoretical kinetic model gave a first order with respect to oil triglycerides. In this case, the activation energy was found to be 71.83 kJ/mol and pre-exponential factor was found to be 2.48 x1010. More investigation should be done to describe the kinetic behaviour of biodiesel production from non-edible oil in order to confirm the correct reaction order and why there is change in reaction order when the temperature increases above 60°C. / MT2018

Thesis (Master of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2019. / The biodiesel industry produces large volumes of biodiesel wastewater (BDWW) during the purification of crude biodiesel. This wastewater is characterised by high concentrations of chemical oxygen demand (COD), biological oxygen demand (BOD), total suspended solids (TSS), and fats, oils and greases (FOG) which in turn defines BDWW as a highly polluted effluent. The low nitrogen and phosphorous content of BDWW creates an unfavourable environment for the growth of microorganisms, thereby making it difficult to degrade naturally. Biodiesel companies discharge untreated non-compliant wastewater directly to the municipal sewer system. Treatment prior to discharge is a necessity since the disposal of untreated BDWW may raise serious environmental concerns (i.e. disturbance of biological ecosystems) resulting in penalties liable by non-compliant companies due to the implementation of the waste discharge charge system (WDCS) which is regulated by the industrial waste discharge standard limits in South Africa (SA). This study aimed to combine the advantages of the conventional anaerobic baffled reactor (ABR) system with microbial fuel cell (MFC) technology resulting in an innovative technology used to treat high strength industrial BDWW at ambient conditions. Many studies have reported effective treatment of BDWW, however to date literature implementing an ABR equipped with MFC technology has not been reported. The main objectives of the study were to determine which parameters do not meet the industrial wastewater discharge standard limits, whether pH and carbon:nitrogen:phosphorous (C:N:P) ratio adjustments will suffice prior to treatment with the ABR-MFC, the maximum power density (PD) as well as to determine the treatment efficiency of the ABR-MFC.

Orientador: Afonso Lopes / Banca: Daniel Junior de Andrade / Banca: Marcílio Vieira Martins Filho / Banca: Gilberto Hirotsugu Azevedo Koike / Banca: Leomar Paulo de Lima / Resumo: O biodiesel de babaçu pode contribuir para a substituição do diesel. A hipótese levantada foi que o uso do diesel B S1800 e B S50, e proporções de mistura com biodiesel de babaçu não alterassem o desempenho do trator agrícola e não comprometessem seu funcionamento. Os objetivos foram avaliar a potência na barra de tração, a velocidade de deslocamento, os consumos de combustível: horário ponderal, volumétrico e específico, e também a opacidade da fumaça. O experimento foi desenvolvido na UNESP/FCAV - IPBEN - Unidade de Ensaio de Máquinas, do departamento de Engenharia Rural - Jaboticabal-SP. No ensaio dinâmico, utilizou-se de um trator de teste que percorreu três parcelas de 40 m espaçadas de 15 m, no final dos percursos o trator foi estacionado e mediu-se a opacidade da fumaça. O biodiesel de babaçu apresentou 11,1% e 14,3% de aumento no consumo específico e redução de 68,6% e 58% na opacidade da fumaça, comparado ao diesel B S1800 e B S50, respectivamente. Conclui-se que o biodiesel de babaçu e proporções com diesel B S1800 e B S50 não comprometem o funcionamento do motor do trator agrícola / Abstract: Babassu biodiesel can contribute to the replacement of regular diesel. The hypothesis given was that the use of diesel B S1800 and B S50 and proportions of babassu biodiesel did not alter the performance of agricultural tractors and nor compromise their operation. The objective was to evaluate the power in the drawbar, travel speed, fuel consumption: mass, volume and time specific, as well as the opacity of the exhaust gas. The experiment was conducted at UNESP/FCAV - IPBEN - Machine Testing Unit, at the Rural Engineering Department located in Jaboticabal, SP, Brazil. For the dynamic test, a test tractor was used. It ran three 40 m parcels with a 15 m space between them. At the end of the course, the tractor parked and the opacity of the exhaust gas was measured. When comparing it with the B S1800 and B S50 diesel, the babassu biodiesel showed an 11.1% and 14.3% increase in specific fuel consumption and a reduction of 68.6% and 58% in gas opacity, respectively. Thus, proportions of babassu biodiesel with diesel B S1800 and B S50 do not compromise the operation of tractor engines / Doutor

Orientador: Jane Maria Bertocco Ezequiel / Banca: Márcia Helena Machado de Rocha Fernandes / Banca: Mauro Dal Secco de Oliveira / Banca: Leandro das Dores Ferreira da Silva / Banca: Fábio Prudêncio de Campos / Resumo: Objetivou-se nesse estudo avaliar os efeitos da associação da glicerina ao milho e polpa cítrica na dieta de bovinos da raça Nelore confinados sobre o consumo, digestibilidade, parâmetros ruminais (pH, nitrogênio amoniacal, ácidos graxos de cadeia curta, produção de gases e massa microbiana), desempenho em confinamento, características da carcaça e da carne, parâmetros sanguíneos e comportamento ingestivo. Cinco dietas foram fornecidas e denominadas de: CON - sem adição de glicerina; M10 - milho e 10% de glicerina; M15 - milho e 15% de glicerina; P10 - polpa cítrica e 10% de glicerina; P15 - polpa cítrica e 15% de glicerina. No primeiro experimento foram utilizados cinco bovinos providos de cânulas permanentes no rúmen, distribuídos em delineamento experimental quadrado latino (5 x 5). Nos tratamentos com polpa cítrica (P10 e P15) foram verificados menores consumos e digestibilidades da matéria seca, matéria orgânica, fibra em detergente neutro e fibra em detergente ácido do que nos tratamentos com milho (M10 e M15). Para o tratamento controle houve menor produção do ácido butírico mas, maior produção de ácido acético e totais em relação aos tratamentos com glicerina. A relação acetato:propionato também foi maior no tratamento controle seguida dos tratamentos com polpa cítrica. Também foram observadas reduções nas produções das bactérias ruminais nos tratamentos com polpa cítrica, contudo sem afetar o pH e nitrogênio amoniacal ruminais nem a produção dos gases carbônico e metano. No segundo experimento, trinta bovinos foram confinados e distribuídos em delineamento experimental inteiramente casualizado no qual houve alterações no consumo de amido e fibra solúvel, contudo, sem afetar o desempenho, características da carcaça, nem o comportamento animal. A inclusão de glicerina provocou redução na intensidade de amarelo na carne e aumento no porcentual dos ácidos graxos ... / Abstract: The objective of this study was to evaluate the association of glycerin to corn grain and citrus pulp in diets for Nelore cattle on intake, digestibility, ruminal parameters (pH, ammonia, short chain fatty acids, gas production and microbial mass), performance, characteristics of carcass and meat, blood parameters and feeding behavior. Five diets were provided and named: CON - without addition of glycerin; M10 - corn grain and 10% glycerin; M15 - corn grain and 15% glycerin; P10 - citrus pulp and 10% glycerin; P15 - citrus pulp and 15% glycerol. In the first experiment were used five cattle fitted with permanent rumen cannulas, distributed in Latin Square design (5 x 5). In treatments with citrus pulp (P10 and P15) were observed lower intake and digestibility of dry matter, organic matter, neutral detergent fiber and acid detergent fiber than in treatments with corn grain (M10 and M15). For the control treatment there was decreased production of butyric acid but greater production of acetic acid and totals compared to treatments with glycerin. The acetate:propionate ratio was also higher in the control treatment followed by treatment with citrus pulp. Were also observed decrease in the production of bacterial microorganisms, but without affecting the pH and ruminal ammonia neither the production of methane or dioxide carbon. In the second experiment, thirty cattle were confined and distributed in a completely randomized design. There were changes in the starch and soluble fiber intake, but, without affecting the performance, carcass characteristics, or animal behavior. The addition of glycerin caused reduction in the intensity of yellow in the meat, and increase in the percentage of fatty acids C15:0 and C17:1. About blood parameters only the triglycerides were influenced by the treatments. The concentrations of glucose and gamma-glutamyl transferase (GGT) were higher than suggested by the literature, the high values are probably ... / Doutor

Orientador: Messias Borges Silva / Coorientadora: Marcela Aparecida Guerreiro Machado / Banca: Eliana Vieira Canettieri / Banca: Roney Arismel Mancebo Boloy / Banca: Fabrício Maciel Gomes / Banca: Patrícia Caroline Molgero da Rós / Resumo: O presente trabalho foi desenvolvido com a microalga Chlorella minutissima com o objetivo de determinar as melhores condições operacionais de fotobioreatores tubulares descontínuos, tipo coluna de bolhas, para o crescimento celular e a produção de lipídeos em função das variáveis de processo: fluxo de CO2 na alimentação, concentração inicial de nitrato, concentração inicial de fosfato, suplementação (metais e vitaminas), temperatura e salinidade. Os experimentos foram planejados utilizando a metodologia de Taguchi. Os resultados obtidos mostraram que a configuração do fotobioreatores tubulares descontínuos, tipo coluna de bolhas, foi adequada para o cultivo da microalga Chlorella minutíssima, apresentando bons resultados de teor de lipídeos, da ordem de 37,08 ± 1,50 % em relação à biomassa seca ao final de 7 dias de cultivo. Definidas as condições ótimas de cultivo foi realizada uma reação como o óleo obtido, empregando catalisador químico (H2SO4). O resultado obtido demonstrou que o catalisador atuou de forma eficiente, convertendo os ácidos graxos em seus respectivos ésteres de etila. Outro fator importante de ressaltar foi a ausência de pigmentos presente no material lipídico, visto que o óleo extraído apresentou coloração amarelada similar aos óleos vegetais tradicionais, como por exemplo, o óleo de soja. Pigmentos quando presentes no material lipídico podem comprometer a conversão dos triglicerídeos em ésteres alquílicos (biodiesel). Chlorella minutissima apresenta vant... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The current work was developed with the microalgae Chlorella minutissima with the aim of determining the best operational conditions of discontinuous-tubular photobioreactors, bubble-column type, to the cell growth and production of lipids in relation to process variables: CO2 feed flow rate, nitrate initial concentration, phosphate initial concentration, supplements (metals and vitamins), temperature and salinity. The experiments were designed using Taguchi methodology. Results showed that the configuration of discontinuous-tubular photobioreactors, bubble-column type was adequate to the cultivation of microalgae Chlorella minutissima, presenting good results in terms of lipid content, of order of 37.08 ± 1.50% in relation to the dry biomass at the end of the 7 cultivation days. Once optimal cultivation conditions were established, a reaction with obtained oil was carried out using a chemical catalyst (H2SO4). Results showed that the catalyst acted in an efficient way, converting fatty oils in its respective ethyl esters. Another important factor worth noticing was the absence of pigments present in the lipid material, considering that the extracted oil presented a yellow color similar to traditional vegetal oils, such as soy oil. The presence of pigments in the lipid content may compromise the conversion of triglycerides in alkyl esters (biodiesel). Chlorella minutissima presents additional advantage in comparison to diverse lipid raw materials with the presence of pigments... (Complete abstract click electronic access below) / Doutor

Hydrotreating reaction of vegetable oil is an alternative method for the production of renewable biodiesel fuel. This reaction involves conversion of triglycerides into normal alkanes, leads to a deoxygenated and stable product, which is fully compatible with petroleum derived diesel fuel. The hydrotreating process uses hydrogen to remove oxygen from triglyceride molecules at elevated temperature in the presence of a solid catalyst. This work focused on the development of microtechnology-based chemical reaction process for liquid biofuel production from oil-based biofuel feedstock. A hydrotreating reaction of oleic acid and triolein as model compounds and jatropha oil as real feedstock was studied in a continuous flow microchannel reactor of inner diameter 500 ��m and of varied length; 1.5 - 5 m. The microchannel reactor was fabricated from SS-316. The walls of the microreactor were coated with a thin Al���O��� film, which was then impregnated with Ni-Mo catalyst containing phosphorus as promoter. The reactions were carried out in the temperature range of 275-325 ��C, residence time in the range of 11-40 s and at constant system pressure of 500 psig. The results showed that the microchannel reactor was suitable for the hydrotreating process. Complete conversion of the fatty acid hydrotreating reaction was achieved at a reaction temperature of 325 ��C. Hydrotreating of fatty acids occurred primarily via hydrodeoxygenation and the main liquid products were octadecane and heptadecane. Fatty alcohol, fatty acid and long chain esters were formed as reaction intermediates. Hydrotreating of triglycerides proceeded via the hydrocracking of triglycerides into diglycerides, monoglycerides and fatty acids. Then fatty acids were subsequently deoxygenated to hydrocarbons. The conversion of fatty acids and triglycerides increased with increasing temperatures. A detailed mathematical model was developed to represent this two-phase chemical reaction process. The mathematical model was entirely based on first principles, i.e. no adjustable or correlation parameters were used. Kinetic parameter estimation was performed and the predicted results were in good agreement with experimental results. / Graduation date: 2013 / Access restricted to the OSU Community, at author's request, from Sept. 17, 2012 - Sept. 17, 2013

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Thesis (M.Sc.)--Victoria University of Wellington, [2008] / Includes bibliographical references.