virgen en spray para cocinar y para consumo directo. Utilizará una novedosa tecnología que evita el contacto entre el gas y el aceite y se orienta a un segmento de la sociedad que busque un producto saludable y de propiedades organolépticas agradables. Con relación al mercado para este producto el consumo interno va en aumento gracias a una tendencia creciente a consumir productos de estas características, proyectando al 2021 una demanda potencial de 807 toneladas de este producto. Sin embargo, considerando la competencia en el sector al que se dirige este producto y su intención e intensidad de compra, estimamos que la demanda del proyecto para el 2017 será de 21.46 toneladas del producto y para el 2021, 53 toneladas. Respecto a la localización de la planta, la provincia más adecuada luego de realizar un ranking de factores es Arequipa. Esto se debe a que, junto con Tacna, su producción de aceitunas es la más alta del Perú y la cercanía a la materia prima es vital. Su mayor proximidad a Lima a comparación a Tacna es lo que la define como el lugar más adecuado. La planta se localizará en el distrito Arequipa. / Trabajo de investigación

Les huiles végétales et leurs dérivés ont conduit à de nouveaux précurseurs agro-ressourcés utilisés pour la synthèse de polymères. Grâce au couplage thiol-ène, des polyols ont été obtenus par greffage du mercaptoéthanol directement sur les triglycérides insaturés. De la même manière, les esters méthyliques des huiles végétales ont permis la synthèse d'esters et d'amides diols pseudo-téléchéliques. Des polyols ont également été obtenus grâce à la réaction d'ouverture des cycles oxirane présents sur des huiles végétales époxydées. Différents acides carboxyliques ont permis d'introduire des fonctions hydroxyle sur les triglycérides. Ces différents synthons ont conduit à l'élaboration d'une large gamme de matériaux polyuréthanes, présentant des Tg variant de -10 °C à 100 °C. Le carbonate de glycérol, issu du glycérol agro-ressourcé, a également été utilisé pour l'élaboration de dicyclocarbonates, soit par estérification/trans-estérification à partir de diacides obtenus par greffage de l'acide thioglycolique sur plusieurs acides gras, soit par dimérisation à partir d'un dithiol commercial. Des polyuréthanes sans isocyanate ont ainsi été formulés à partir de ces nouveaux dicyclocarbonates, ouvrant la voie vers des polyhydroxyuréthanes totalement agro-ressourcés. Les précurseurs, ainsi que les matériaux qui en découlent, ont été caractérisés et certains ont fait l'objet de tests à l'échelle pré-industrielle. / Vegetable oils and their derivatives were used to synthesize new precursors suitable for polymer synthesis. Mercaptoethanol was grafted onto unsaturated triglycerides by thiol-ene coupling to yield polyols. This functionalization was also applied to vegetable oil methyl esters, yielding ester and amide containing pseudo-telechelic diols. The second synthetic strategy used ring opening of epoxydized vegetable oils. The reaction between vegetable oil oxiranes and several carboxylic acids afforded a range of polyester polyols. Thus, the synthesized intermediates allowed to formulate various polyurethanes, which exhibited glass transition temperatures ranging from -10 °C to 100 °C. Moreover, either esterification/trans-esterification with fatty acid based diacids, synthesized by thioglycolic acid addition onto different fatty acids, or thiol-ene coupling with a commercial dithiol, were performed on glycerin carbonate, leading to new dicyclocarbonates. Isocyanate free polyurethanes were then obtained from those dicyclocarbonates, opening the way for fully biobased polyhydroxyurethanes. The new precursor, and the polymers therefrom, were deeply characterized and some of them were tested at a pilot scale.

No presente trabalho são relatados os resultados obtidos de ensaios de ressonância magnética nuclear, número de acidez, índice de iodo, índice de saponificação, calorimetria exploratória diferencial com pressão (PDSC), viscosidade e curvas de resfriamento para dois tipos de óleos vegetais, o de soja e o de dendê. Esses ensaios foram efetuados em amostras de óleos puras e também em formulações com diferentes antioxidantes em diferentes concentrações em massa. Basicamente duas situações foram avaliadas, a condição óleo novo e a condição óleo oxidado. A condição oxidada foi obtida por meio de ensaios de oxidação acelerada. Uma análise desses resultados permitiu verificar que o óleo de soja foi mais sensível ao envelhecimento (oxidação) e que os aditivos de melhor desempenho foram o Irganox L109 com 5 % em massa para o óleo de soja e o Galato de Propila com 2 % em massa para o óleo de dendê. / In the present work are analyzed results from Nuclear Magnetic Resonance, Acid Number, Iodine Number, Pressure Differential Scanning Calorimetry, Viscosity and cooling curves obtained from 2 types of vegetable oils: soybean and palm. Such tests were performed in the vegetable oil samples with oxidations inhibitors and without those additives. Basically two conditions were evaluated: as not oxidized (new condition) and as oxidized (used condition). Oxidized condition was made by accelerated oxidized test performed in the different vegetable oil samples. Results show that soybean oil is more sensitive to oxidation than palm oil. Irganox L109 (5 %) was the better oxidation inhibitor to the soybean oil and Propil Galate (2 %) had better performance as antioxidant to the palm oil.

Na primeira etapa deste trabalho foram sintetizados novos ligantes do tipo N-piridínicos, derivatizados de cadeias de ácidos graxos, a partir dos óleos vegetais de babaçu e canola in natura, aqui denominados ligantes Graxo-Amida (GA). Estes foram caracterizados por espectroscopia na região de infravermelho (IV) e ressonância magnética nuclear de hidrogênio e carbono (RMN 1H e 13C). Os ligantes foram coordenados a centros de rutênio do tipo cis-[RuCl2(LL)2] onde LL = 2,2\'-bipiridina, em que os ligantes cloro foram substituídos por duas unidades do ligante Graxo-Amida. Os íons complexos obtidos do tipo [Ru(bpy)2(GA)2]2+ foram caracterizados por análise elementar (CHN), IV, voltametria cíclica, espectroscopias eletrônicas de absorção e emissão e RMN (1H e 13C). Os voltamogramas obtidos mostraram uma diferença de potencial redox entre o complexo sintetizado com o óleo de canola e o sintetizado com o óleo de babaçu, ao comparar esses resultados com estudos voltamétricos da literatura do íon complexo [Ru(bpy)2(3-Amnpy)2]2+. Observou-se que a composição de ácidos graxos desses óleos vegetais, onde a presença ou não de insaturações, pode influenciar nas propriedades eletrônicas das espécies. O composto mostrou-se estável a presença luz, e não sofreu fotoquímica. A influência do meio em solução foi verificada e os indícios demonstram que os complexos não sofrem solvatocromismo. Os complexos possuem emissão em ~700 nm a 25°C quando excitados em λ480. Numa segunda etapa, monômeros de olefina cíclica do tipo ácido-norborneno foram inseridos nas cadeias de éster metílico, obtidas através da transesterificação do óleo de canola. Essa inserção foi realizada através de anéis oxiranos gerados nas insaturações das cadeias do éster. Reações de polimerização via ROMP foram realizadas com précatalisadores do Grupo, e estes monômeros mostraram alguma atividade frente à polimerização. / In the first stage of this work new N-pyridinic kind of ligands were synthesized, as fatty acids chain derivatized, from babaçu and canola vegetable oils, called fatty-amide ligands (GA). They were characterized by infrared spectroscopy (IR) and hydrogen and carbon nuclear magnetic resonance (1H and 13C NMR). The ligands were coordinated to cis-[RuCl2(LL)2] ruthenium center kind, where LL = 2,2\'-bipyridine, in which chlorine ligands where replaced by two fatty-amide ligand units. The obtained [Ru(bpy)2(GA)2]2+ complex kind were characterized by elemental analysis (CHN), IR, cyclic voltammetry, electronic absorption and emission spectroscopy and 1H and 13C NMR. The obtained voltammograms showed redox potential difference between the canola oil synthesized complex and the babaçu oil synthesized complex, when compared to the complex ion [Ru(bpy)2(3-Amnpy)2]2+ voltammetrics studies present in literature. It was observed that the vegetable oil fatty acids composition, in terms of insaturations presence or absence, have electronic influence on the species. The compound was stable at presence of light and suffered no photochemistry. The solution solvent was verified and there were no signs of solvatochromism. The complexes exhibited ~700 nm emission at 25 °C. In a second stage, norbonene acid cyclic olefin monomers kind were inserted in the methylic ester chains, obtained through canola oil transesterification. ROMP polymerization reactions were performed with our research group\'s precatalyst and these monomers showed some activity due to the polymerization.

[pt] A determinação de Na, K, Ca e Mg é parte da caracterização do biodiesel puro (B100) ou misturas com diesel de petróleo (B2, B5, B10, etc). A determinação desses elementos é necessária, pois a sua presença acima de certos níveis pode alterar as características de uso do produto. Desta forma, são apresentados nesta tese os estudos de otimização e validação que deram suporte à elaboração da norma ABNT NBR 15556, e também a comparação do desempenho de técnicas analíticas como a LS F AAS e HR-CS AAS na aplicação desta norma para a determinação de Na, K, Mg e Ca em biodiesel. Uma vez que outros elementos provavelmente virão a fazer parte daqueles cuja determinação será necessária para caracterização do biodiesel, é aqui também apresentado o desenvolvimento de métodos para a determinação de As e Si em óleos vegetais e biodiesel. Assim, neste trabalho, ficou comprovado que Na, K, Ca e Mg podem ser determinados em biodiesel obtidos de diferentes matérias-primas pela técnica de F AAS, com limites de detecção adequados para a sua caracterização de acordo com a legislação vigente. No caso do As, o método proposto para a determinação em amostras de óleo vegetal e biodiesel por GF AAS é simples, rápido, preciso e adequado para os limites esperados da legislação brasileira. As amostras, preparadas como uma solução de três componentes com solução de ácido nítrico e propanol-1, mostraram boa estabilidade, o que permitiu a automação do procedimento pelo uso de amostradores automáticos. Para o Si, os resultados indicam que é possível realizar a determinação em amostras de óleo vegetal e de biodiesel usando a técnica de HR-CS F AAS, após uma simples diluição da amostra com xileno, utilizando-se calibração externa com soluções de calibração preparadas em solução de óleo de base em xileno, para ajuste de viscosidade. / [en] The determination of Na, K, Mg and Ca is part of pure biodiesel (B100) or petroleum diesel blends (B2, B5, B10 etc) characterization. Thus, the determination of these elements is necessary, since their presence above certain levels can change the characteristics of use of the product. This thesis presents optimization and validation studies that support the ABNT NBR 15556, and also the comparison of the performance of LS F AAS and HR-CS AAS in applying this norm for the determination of Na, K, Mg and Ca in biodiesel. Since other factors are likely to become required determinations in biodiesel characterization, this study also presents methods developed for the determination of As and Si in vegetable oils and biodiesel. This study confirmed that Na, K, Mg and Ca can be determined in biodiesel samples obtained from different origins by F AAS, with adequate limits of detection for their characterization according to the current legislation. The proposed method for the determination of As in vegetable oil and biodiesel samples by GF AAS is simple, quick, precise and adequate for the expected limits in Brazilian legislation. The samples, prepared as a three-component solution, in a 1-propanol and nitric acid solution, showed good stability, allowing the automation of the procedure by use of automatic samplers. Low volatile and toxicity solvents were used, allowing external calibration to be performed with standard inorganic or organometallic As solutions. For Si, results indicate that it is possible to perform this elements determination in vegetable oil and biodiesel by HR-CS F AAS, after simple sample dilution with xylene, using external calibration with calibration solutions prepared in a base oil in xylene solution, for viscosity adjustment.

The aim of the diploma thesis was determined the particular fatty characteristics of various vegetable oils in dependence on their storage life and storage conditions. Storage conditions were defined by room temperature and coolroom temperature. The fourteen oils were used for analyses, namely linseed oils, castor oil, grape seed oil, almond oil, olive oil, jojoba oil, avocado oil, apricot kernel oil, corn oil, rice bran oil, macadamia nut oil, soya bean oil, pumpkin seed oil and sunflower oil. All tested oils were supplied by firm M+H, Míča a Harašta s.r.o. The fatty characteristics included the saponification value, the acid value, the iodine value and the thiobarbituric value. The ester values and the percentage glycerol content were counted on the basis of the saponification value and the acid value. Time dependences of all fatty characteristics were figured to graphs and they were compared on various storage conditions. The fatty characteristics indicated lower values in storage of oil samples in coolroom than at laboratory temperature.

The aim of the diploma thesis was the identification of fatty acids contained in vegetable oils by gas chromatography. Amount of fatty acids was monitored in dependence on the duration and conditions of storage. Conditions for storage were selected at room temperature and refrigerator temperature. In total fourteen oils were analyzed - avocado oil, pumpkin seed oil, grape seed oil, jojoba oil, corn oil, linseed oil, macadamia oil, almond oil, apricot-stone oil, olive oil, castor oil, rice oil, sunflower oil and soya bean oil. Gas chromatography was applied for identification and quantification of fatty acids. Methanol esterification method using potassium hydroxide catalysis was chosen for preparing of the samples of the fatty acid methylesters. Eight fatty acids were observed in the vegetable oils : myristic, palmitic, palmitoleic, stearic, oleic, linoleic, gama-linolenic and linolenic acids.

M. Tech. (Department of Chemistry, Faculty of Applied And Computer Sciences), Vaal University of Technology. / Biodiesel has an ability to solve the problem associated with the use of fossil fuels as a source of energy. The aim of this study was to produce biodiesel from waste cooking oil (WCO) by transesterification, catalysed with potassium hydroxide (KOH) supported on attapulgite (ATP) clay as the heterogeneous catalyst. WCO was used on the basis that it is one of the cheapest feedstocks for biodiesel production, is readily available and can minimise environmental impact. ATP clay was first crushed and sieved to particle sizes of ≤ 90 μm and subsequently treated with hydrochloric acid (HCl) to remove impurities. The KOH supported ATP catalyst was prepared through ion exchange method by soaking ATP into KOH solution, dried in an oven and later calcined at 400 ℃ in a furnace. The prepared catalyst and ATP clay were characterised using Hammett indicator to determine the basic strength of the catalyst. XRF and EDX were used to determine the elemental composition of the catalyst whilst XRD was used to determine the crystallinity of the ATP after modification. The functional groups of ATP were determined by FTIR. BET was utilised to determine the changes on the surface area, pore volume and pore diameter of ATP and on the other hand, SEM was used to determine the morphological changes on the surface of ATP. The XRD, FTIR, BET AND SEM-EDX showed that addition of potassium caused changes on the surface of the ATP. The optimal conditions for the transesterification reaction of waste cooking oil with methanol were found to be oil-to-methanol molar ratio of 1:15, 3wt% catalyst amount, 65 ℃, 3 h of a reaction time, at 200 rpm stirring rate and 94 % biodiesel yield was obtained. After the catalyst was reuse three consecutive times, the decrease in biodiesel yield was observed (Figure 17) after each cycle. However, the 5MKOH/ATP catalyst is heterogeneous and can be used to transesterify WCO with good yield.

Thesis submitted in 50 % completion of the degree of Master of Management in the field of Public and Development Management at the University of the Witwatersrand, Johannesburg. 20 June 2016 / In response to the ever increasing problems associated with climate change, and greenhouse gas emissions, many countries in the world are developing and adopting climate change resilient policies that support green economy. Green economy sector in South Africa has not as yet received much expected attention as a key sector to address economic and environmental problems. The use and the production of renewable fuels, such as biodiesel are known to have significant economic and environmental benefits. However, progress in the production of biodiesel is hampered by limits imposed by government on the use of fresh vegetable extracted oils for production of biodiesel, mainly due to challenges on food security; and the impact this will have on food prices. In recent years recycling has become an important tool to address waste problems; pollution control; and socio-economic problems such as joblessness, poverty and social inequity. Used cooking oil has always been considered waste and an environmental burden. Therefore through technology advancement of recycling, wastes such as used cooking oil have become useful resources for biodiesel production. This research is about the challenges in recycling used cooking oil to produce biodiesel. The study recommended that in order to address challenges facing sustainability of our environment, and high unemployment rate; small recycling industries such as those operating in Polokwane will need government support such as biodiesel sector policies and regulations, to encourage investment in the biodiesel value chains in a way that will lead to the achievement of green economy goals. / MT2016

No / Biodiesel has turned out to be an integral part of the discussion of renewable energy sources and has diverse advantages in terms of its flexibility and applicability. Considering the characteristics of the transesterification reaction, a laboratory-scale system has been developed in this work. Waste Vegetable Oil (WVO), mainly sunflower oil, from local sources has been used and the transesterification carried out using methanol in the presence of sodium hydroxide catalyst. Characterisation of the biodiesel produced has been carried out using a number of different techniques including rheology, calorimetry, and gas liquid chromatography. The main factors affecting the % yield of biodiesel are temperature, catalyst, and alcohol to triglyceride ratio. Thus, experimental work has been carried out so as to study the rate and yield of the reaction as a function of those factors. A model has also been developed to validate the experimental data and this should help in increasing the efficiency of these processes and reducing the energy input. Moreover, the novel use of ultrasound as a method of measuring progression of the reaction is correlated with in-situ pH monitoring of the reaction process.