Dissertations / Theses on the topic 'Steam distillation'

Recent experimental and simulation studies -conducted at the Department of Petroleum Engineering at Texas A&M University - confirm oil production is accelerated when propane is used as an additive during steam injection. To better understand this phenomenon, distillation experiments were performed using seven-component synthetic oil consisting of equal weights of the following alkanes: n-C5, n-C6, n-C7, n-C8, n-C9, nC10, and n-C15. For comparison purposes, three distillation processes were investigated: dry-, steam-, and steam-propane-distillation, the latter at a propane:steam mass ratio of 0.05. The injection rate of nitrogen during dry-and steam-distillation was the same as that of propane during steam-propane distillation, 0.025 g/min, with steam injection rate kept at 0.5 g/min. The distillation temperatures ranged from 115°C to 300°C and were increased in steps of 10°C. The cell was kept at each temperature plateau (cut) for 30 minutes. Distillation pressures ranged from 0 psig for dry distillation to 998 psig for steam-and steam-propane distillation. The temperature-pressure combination used represented 15°C superheated steam conditions. Distillate samples were collected at each cut, and the volume and weight of water and hydrocarbon measured. In addition, the composition of the hydrocarbon distillate was measured using a gas chromatograph. Main results of the study may be summarized as follows. First, the hydrocarbon yield at 125°C is highest with steam-propane distillation (74 wt%) compared to steam distillation (58 wt%), and lowest with dry distillation (36 wt%). This explains in part the oil production acceleration observed in steam-propane displacement experiments. Second, the final hydrocarbon yield at 300°C however is the same for the three distillation processes. This observation is in line with the fact that oil recoveries were very similar in steam- and steam-propane displacement experiments. Third, based on the yields of individual hydrocarbon components, steam-propane distillation lowers the apparent boiling points of the hydrocarbons significantly. This phenomenon may be the most fundamental effect of propane on hydrocarbon distillation, which results in a higher yield during steam-propane distillation and oil production acceleration during steam-propane displacement. Fourth, experimental K-values are higher in distillations with steam-propane for the components n-hexane, n-heptane, n-octane, and n-nonane. Fifth, vapor fugacity coefficients for each component are higher in distillations with steam-propane than with steam. Finally, Gibbs excess energy is overall lower in distillations with steam-propane than with steam. The experimental results clearly indicate the importance of distillation on oil recovery during steam-or steam-propane injection. The experimental procedure and method of analysis developed in this study (for synthetic oil) will be beneficial to future researchers in understanding the effect of propane as steam additive on actual crude oils.

Simulation study has shown oil production is accelerated when propane is used as an additive during steam injection. To better understand this phenomenon, distillation experiments were performed using San Ardo crude oil (12oAPI). For comparison purposes, three distillation processes were investigated: dry-, steam-, and steam-propanedistillation, the latter at the propane-to-steam mass ratio of 0.05 at steam injection rate 0.5 g/min. Two sets of the distillation experiments were carried out. In the first set of experiments, the distillation temperatures ranged from 115ºC to 300ºC. Distillation pressures ranged from 0 psig to 998 psig for steam- and steam-propane distillation. The temperature-pressure combination used represented 15ºC superheated steam conditions. In the second set of experiments, the distillation temperatures ranged from 220oC to 300oC at 260 psig. The temperature pressure combination used represented field conditions for crude oil. For both conditions, the cell was kept at each temperature plateau (cut) until no increase occurs in distillation yields. Distillation yields were collected at each cut, and the volume and weight of water and hydrocarbon measured. Based on these experiments, a thermodynamic modeling framework was developed that describes distillation effect and oil production for steam distillation experiments. The model is based on composition of crude oil, molecular weight of heavy fraction. The analytical model results are compared against the experimental data for synthetic crude and crude oil to verify the validity of the model. Main results of the study may be summarized as follows. The yields for steam distillation for saturated conditions of Tsat+15 o C and Psat is 10 % and with addition of 5% of propane to steam no significant increase occurs in distillation yields. The yields for steam distillation for field conditions of 260 psig and temperature range (220 ~300oC) is 18 % and with addition of 5% of propane to steam no significant increase in distillation yields. The results indicate that propane has minimal distillation effect on the heavy oil. This occurs possibly because of lesser amount of light fractions in the heavy oil that enhance the separation of components in the oil caused by the concentration gradient.

The production of essential oil has remained unchanged for decades. In the face of increased competition from low cost suppliers the requirement to reduce the cost of production is facing many producers. The application of a counter-current system to the steam distillation of essential oils the transition from traditional production methods to more efficient methods was evaluated. Modelling a system using existing mathematical models found in the literature provided a basis for the comparison between the old and the new. The question of the conversion of operating principles was met with the findings that the system is immature in inception. Further research is required to address the technical issues of introducing and removing plant material from a distillation column without interrupting the flow of steam. Initial bench tests have confirmed the benefits of moving to a non-batch system, this research is in its infancy with many further tests required to cement the findings of this thesis. Substantial portions of this thesis have been redacted or limited details provided, as large sections of the research are of a confidential nature.

Thermal recovery methods are frequently used to enhance the production of heavy crude oils. Steam-based processes are the most economically popular and effective methods for heavy oil recovery for several decades. In general, there are various mechanisms over steam injection to enhance and have additional oil recovery. However, among these mechanisms, steam distillation plays pivotal role in the recovery of crude oil during thermal recovery process. In this study, an experimental investigation was carried out to investigate the role of various minerals present in both sandstone and carbonate formations as well as the effect of steam temperature on steam distillation process. Two different types of dead-heavy crude oils were tested in a batch autoclave reactor with 30 % water and the content of the reactor (crude oil, 10 % rock and mineral). The results were compared as the changes in the density, viscosity and chemical composition (SARA and TPH analyses) of heavy crude oil. Five different mineral types (bentonite, sepiolite, kaolinite, illite and zeolite) were added into the original crude oil and reservoir rocks to observe their effects on the rheological and compositional changes during steam distillation process. Analysis of the results of experiments with Camurlu and Bati Raman heavy crude oils in the presence of different minerals such as Bentonite, Zeolite, Illite, Sepiolite, and Kaolinite in both sandstone and limestone reservoir rocks indicate that steam distillation produces light end condensates which can be considered as solvent or condensate bank during steam flooding operation. It was also illustrated that minerals in reservoir formations perform the function of producing distilled light oil compounds, resulting in enhancement of heavy crude oils recovery in steam flooding. Measurements showed that the remaining oil after steam distillation has higher viscosity and density. On the other hand, the effect of steam distillation is more pronounced in limestone reservoirs compared to sandstone reservoirs for the given heavy crude oil and steam temperature. Among the five different minerals tested, kaolinite found to be the most effective mineral in terms of steam distillation.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Nitrogen (N) fertilization management in the states of Rio Grande do Sul (RS) and Santa Catarina (SC), Brazil, is performed using interpretation tables of soil organic matter (SOM) in which we obtain the interpretation ranges of N availability and therefore N rates. However, the productivity of flooded rice is highly variable according to the SOM content, resulting low and high relative grain yields regardless of the SOM content or N fertilization. Soil analysis methods estimate the labile organic N, which is mineralizable and may be available during the crop cycle. Moreover, these methods have the potential to obtain a better correlation between the amount of soil analysis and crop productivity. Therefore, this study aims to evaluate the ability of alkaline hydrolyzable N content extracted by Direct Steam Distillation (DSD) method of analysis to predict N mineralization in paddy soils from RS state. We collected 32 soil samples (0-20 cm layer) in the five rice production areas of RS state, which presented some contrasting texture and SOM content. The DSD method was used to obtain the mineralizable N content in the soil samples. We carried out a laboratory experiment to determine the N mineralization in anaerobic incubation, and another greenhouse experiment to determine the content and the accumulation of N by rice plants. We evaluated the Pearson linear correlation coefficient (r) (P <0.05) between the N content available after 28 days of anaerobic incubation and the N accumulation by rice plants with the N content obtained by DSD, SOM, total N and clay contents. The results of N estimated by DSD, N mineralized under anaerobic incubation and N accumulated by plants showed high amplitude, which was linked to the attributes of the soil samples. Results have shown that the evaluation of a more labile fraction of N by the DSD method improves the estimation of N availability when compared to the methods that assess the total SOM. This method has the potential to be used as indicator of the N availability in paddy soils in the RS state. The soil clay content influenced mineralization, availability and accumulation of N by rice plants, suggesting the necessity to include this soil parameter in the calibration, interpretation and/or recommendations of N fertilization for flooded rice.
O manejo da adubação nitrogenada nos estados do Rio Grande do Sul (RS) e Santa Catarina (SC) é realizado por meio de tabelas de interpretação do teor de matéria orgânica do solo (MOS), a partir do qual se obtêm as faixas de interpretação da disponibilidade de nitrogênio (N) e, consequentemente, as doses de N. No entanto, a produtividade do arroz irrigado por inundação é muito variável com o teor de MOS, sendo obtidos tanto baixos como elevados rendimentos relativos da cultura, independente do teor de MOS ou da adubação nitrogenada aplicada. Métodos de análise do solo que estimam frações lábeis de N orgânico, prontamente mineralizáveis e que podem ser disponibilizadas durante o ciclo da cultura, têm potencial para auxiliar na obtenção de uma melhor correlação entre o valor da análise do solo e a produtividade da cultura. Diante disso, o presente estudo visa avaliar a capacidade do teor de N alcalino hidrolisável, extraído pelo método de análise Direct Steam Distillation (DSD), em predizer a mineralização de N em diferentes solos aptos ao cultivo de arroz irrigado do RS. Foram coletadas 32 amostras de solo na camada de 0 - 20 cm, abrangendo as cinco regiões produtoras de arroz do RS, com diferenças na textura e teor de MOS. Posteriormente, foi utilizado o método DSD para obter o índice de N mineralizável nos solos. Um experimento foi conduzido em laboratório para determinar a mineralização de N em incubação anaeróbica e outro experimento foi realizado em casa de vegetação, para determinar o teor e o acúmulo de N pelas plantas de arroz irrigado. Avaliou-se o coeficiente de correlação (r) linear de Pearson (P<0,05) entre o teor de N disponível após 28 dias de incubação anaeróbica e o conteúdo de N acumulado pelas plantas de arroz com a quantidade de N obtida pelo DSD, teores de MOS, N total e argila. O teor de N estimado pelo DSD, N mineralizado em incubação anaeróbica e o N acumulado pelas plantas apresentaram elevada amplitude, a qual esteve atrelada aos atributos dos solos. Os resultados encontrados apontam que a avaliação de uma fração mais lábil do N pelo método DSD melhora a estimativa da disponibilidade de N em comparação com métodos que avaliam o teor total de MOS, demonstrando que este índice tem potencial de ser utilizado para indicar a disponibilidade de N em solos sob cultivo de arroz irrigado por inundação no estado do RS. O teor de argila do solo influenciou a mineralização, disponibilidade e acúmulo de N pelas plantas de arroz, sugerindo a necessidade de se incluir este parâmetro do solo na calibração, interpretação e/ou recomendações do fertilizante nitrogenado para a cultura do arroz irrigado.

This thesis deals with the batch controlling of a distillation column model. The thesis is divided into several parts. The first part, which is more theoretical, summarizes the description of the batch controlling, the distillation process and the equipment used, including the model of the distillation column itself. The second part is focused on the practical implementation. The beginning of this part displays different types of the models produced by the Standard 88. This section is followed by a description of a device database in the environment of FactoryTalk Batch Equipment Editor, creation of a logical phase codes using functions of the PhaseManager in the environment of RSLogix5000 and a creation of a recipe in the environment of FactoryTalk Batch Recipe Editor. The last part of this thesis deals with the visualization created in the FactoryTalk View Studio SE and final testing of the entire process.

Le monde a connu une augmentation exponentielle de l’énergie; ces demandes sont principalement couvertes par les combustibles fossiles. Cependant, compte tenu des conditions non durables d'une telle source telles que la rareté et les effets environnementaux nocifs, les chercheurs ont dirigée leurs attention vers la rechercher de nouvelles sources d'énergie alternatives. L'énergie solaire est une énergie renouvelable propre, abondante et facilement disponible. L'utilisation de l'énergie solaire pour des applications thermiques offre la possibilité de plusieurs études sur l'énergie, les avantages et l'analyse des bio-composés. Dans le présent travail, le séchage solaire et l'extraction solaire ont été envisagés pour une application expérimentale utilisant deux matrices; feuilles de romarin comme plantes aromatiques et médicinales et écorces d'orange comme sous-produit. Pour l'extraction solaire, une unité de distillation couplée à un réflecteur solaire a été utilisée afin de désodoriser les feuilles de romarin par distillation par entrainement à la vapeur et de valoriser les écorces d'orange ciblant une bio-raffinerie zéro déchet par hydro-distillation. Les avantages de l'extraction d'énergie solaire thermique sont remarquables, permettant une diminution d'environ 37% du temps d'extraction pour les deux matrices étudiées par rapport aux procédés conventionnels. En termes de qualité, plusieurs analyses ont été réalisées afin de comparer les systèmes solaires thermiques et conventionnels. Le rendement et la qualité de l'huile essentielle de romarin et d'écorce d'orange obtenus par GC/MS étaient relativement similaires pour les deux processus. Cependant, les antioxydants dosés par HPLC-DAD présents dans les feuilles de romarin étaient mieux conservés après extraction solaire. Dans l'ensemble, les résultats indiquent que la distillation solaire-vapeur (SSD) est une alternative écologique, efficace et économique pour l'extraction des huiles essentielles et la désodorisation des feuilles. La pectine et les flavonoïdes des pelures d'orange (principalement la narirutine et l'hespéridine) ont également été mieux conservés après le processus d'hydro-distillation solaire. Pour le séchage, un processus conventionnel en couche mince a été envisagé, l'étude expérimentale de cette section s'est concentrée sur l'influence des températures de séchage sur la perte en eau des matrices fraîches séchées à différentes températures, 40 °C, 50 °C, 60 °C, 70 °C pour les feuilles du romarin et 60 ° C, 65 ° C, 70 ° C, 75 ° C °, 80°C pour les écorces d'orange. Ce travail présente les résultats de l'étude expérimentale de la cinétique de séchage. Les résultats sont utilisés pour déterminer la courbe caractéristique de séchage et simuler par des modèles mathématiques le comportement de séchage des feuilles de romarin ou des écorces d'orange afin de trouver le modèle le mieux adapté. Dans l'ensemble, l'extraction solaire et le séchage par convection se sont révélés être des procédures fiables qui préservent la qualité du produit et peuvent être utilisées efficacement comme alternative aux procédés conventionnels
The world has witnessed an exponential increase of energy; those demands are mainly covered by fossil fuels. However, giving the unsustainable conditions of such source such as scarcity and harmful environmental effects, researchers were required to investigate newer alternative power sources. Solar energy is a clean, abundant and easily available renewable energy. It is also one of the most economical alternatives with outstanding processes and applications diversity machineries. Usage of solar energy for thermal applications provides a scope for several studies on energy, benefits, and bio-compounds analysis. The main objectives of this thesis are to promote the use of solar energy for extraction and drying applications, to confront them with the conventional technique usually used, and to better understand the process, outcomes and benefits of such green and sustainable source. Two matrices were considered: rosemary leaves as aromatic and medicinal plants and, orange peels as by-product. For solar extraction a distillation unit coupled with a solar reflector was used to deodorize rosemary leaves via steam distillation and to valorise orange peels targeting a zero-waste bio-refinery via hydro-distillation. The advantages of thermal solar energy extraction are noteworthy, allowing approximately 37 % decrease of extraction time for both the studied matrices in comparison to conventional processes. Quality wise, several analyses were carried in order to compare thermal solar and conventional systems. The rosemary and orange peels essential oil yield and quality obtained by GC/MS was relatively similar for both processes. However, antioxidants assayed by HPLC-DAD present in rosemary leaves were better preserved after solar extraction. Overall, the results indicate that Solar-Steam-Distillation (SSD) is a green alternative, efficient and economical process for essential oil extraction and leaves deodorization. Orange peels pectin and flavonoids (mainly narirutin and hesperidin) were also better preserved after solar hydro-distillation process. For drying, the study was performed on rosemary leaves and orange peels by thin convective solar drying to valorize these matrices, to increase their shelf-life, and to investigate the impact of solar drying on their antioxidant properties. The experimental study focused on the influence of drying temperatures on water loss and quality of fresh matrices dried at different temperatures: rosemary leaves (40°C, 50°C, 60°C, 70°C) and orange peels (60°C, 65°C, 70°C, 75°C°, 80C). Obtained results showed that Midilli– Kucuk and two terms were the most fitted and appropriate models to describe the convective solar drying kinetics of rosemary leaves and orange peels respectively. For rosemary leaves, it was found that with solar drying (40, 50, 60°C, and sun-dried) an increase of carnosol was observed, coupled with a decrease of carnosic acid values; while at high temperature (70°C) both carnosic acid and carnosol contents decrease. This could imply that high temperature may lead to quality deterioration of rosemary leaves. Moreover, at 70°C Total polyphenols (TPC) values decrease and the IC50 value increased illustrating the negative effect of high drying temperatures on rosemary leaves. Contrary to rosemary leaves, the results showed that TPC and DPPH degradation was elevated in both 60°C, 65°C and the natural shade dried orange peels in comparison to high temperatures 75°C, and 80°C.This may state that the product gives better TPC and DPPH concentration if being dried at high temperature. As for the DPPH analysis, it was found that starting from 75°C, the antioxidant activity improves. This may be due to the new substances formation or precursor that occurs between several molecules via non-enzymatic inter-conversion at 70 °C for citrus fruits. Thus, stating that drying at high temperature may be a way to improve the phenolic extraction of orange peels

Este trabalho aborda a modelagem matemática do processo de extração de óleos essenciais por arraste a vapor e a otimização deste processo em escala industrial. Utilizouse dados experimentais de óleos essenciais de alecrim e citronela obtidos em uma unidade industrial de extração por arraste a vapor. O modelo é constituído de um sistema de equações diferenciais parciais, que representam o balanço de massa unidimensional nas fases vapor e sólido. Para resolver o modelo desenvolvido, utilizouse o método das linhas com o uso da técnica de diferenças finitas para discretizar a coordenada espacial e suas derivadas, resultando em um sistema de equações diferenciais ordinárias implementado no simulador EMSO. Os parâmetros do modelo foram estimados pelo método dos poliedros flexíveis, utilizando dois conjuntos de dados experimentais e um terceiro para sua validação. O modelo ajustou-se bem aos dados experimentais industriais, resultando, para duas condições ambientais e geográficas das plantas aromáticas de alecrim, em coeficiente global de transferência de massa de 8,64 x 10 -4 s -1 e 9,10 x 10 -4 s -1, e a constante de equilíbrio de 2,72 x 10 -4 m3=kg e 1,07 x 10 -2m3/kg. Enquanto que para a citronela obteve-se coeficiente global de transferência de massa de 8,29 x 10 -4s -1 e 1,23 x 10 -3 s -1, e constante de equilíbrio de 1,25 x 10 -2 m3/kg e 1,52 x 10 -3 m3/kg. Foi proposto também um problema de otimização para determinar o tempo ótimo de extração e o número de bateladas por dia. Os resultados da otimização do processo indicam que se pode reduzir o tempo de extração, permitindo que outras extrações sejam realizadas por dia, maximizando o volume de óleo extraído ao fim do dia.
This work has as objective the development of a mathematical model of essential oils extraction by steam distillation and the optimization of this process on an industrial scale. We used experimental data obtained from rosemary and citronella in an industrial steam distillation unit. The model consists a system of partial differential equations, which represent the one-dimensional mass balance in steam and solid phases. To solve the developed model, we used the method of lines with the finite differences technique to discretize the spatial coordinate and its derivatives, resulting in a system of ordinary differential equations implemented in the EMSO simulator. The model parameters were estimated by the method of flexible polyhedra, using two experimental runs and a third experimental run to test the model. The model fitted to the experimental data industry, resulting, for two environmental and geographical conditions of rosemary, in mass transfer coefficients of 8,64 x 10 -4 s -1 and 9,10 x 10 -4 s -1, and the equilibrium constant of 2,72 x 10 -4 m3/kg and 1,07 x 10 -2m3/kg. For citronella, the obtained mass transfer coefficient of 8,29 x 10 -4 s -1 and 1,23 x 10 -3 s -1 and equilibrium constant of 1,25 x 10 -2 m3/kg and 1,52 x 10 -3 m3/kg. It was also proposed an optimization problem to determine the optimum extraction time and number of batches per day. The optimization results indicate that the process can reduce the extraction time, allowing other extractions are performed each day, maximizing the essential oil volume extracted in the day.

O tensoativo anfotérico cocoamidopropil betaína (CAPB) é largamente utilizado na indústria de cosméticos, e é considerado um insumo essencial para a formulação de sabonetes líquidos, shampoos e géis de limpeza facial. A síntese deste tensoativo se dá por meio da reação entre ácido graxo de coco e dimetilaminopropilamina (DMAPA) e, posterior reação com o ácido monocloroacético (AMCA). O excesso de DMAPA considerado impureza, precisa ser monitorado devido a sua irritabilidade no contato com a pele, olhos e mucosas podendo em alguns casos provocar dermatite. Atualmente, o método adotado pela empresa Clariant S/A utiliza para a determinação desta substância, cromatografia líquida de alta eficiência (HPLC), entretanto, esta metodologia apresenta elevado tempo de análise e consumo de solventes, comprometendo a produtividade na indústria, por manter os reatores inoperantes na espera do resultado da análise. Existe uma demanda crescente na indústria de cosméticos para utilização de metodologias que abordem critérios de tempo e custo na determinação de impurezas, para assegurar a qualidade dos produtos finais. Assim, com o intuito de aumentar a eficiência no processo de produção, este trabalho tem como objetivo propor um método rápido e confiável por eletroforese capilar para determinar o teor de DMAPA durante a produção (controles de processo) e no produto final do tensoativo CAPB. Neste trabalho foram abordadas diversas técnicas de preparo de amostra e condições instrumentais, para se alcançar um limite de quantificação (LOQ) 10 mg kg-1 (especificação exigida pelo cliente no produto final). O DMAPA foi analisado como cátion, utilizando um eletrólito de corrida com imidazol e HIBA (ácido alpha hidroxibutírico), ambos com concentração de 0,01 mol L-1e pH acertado para 4,0 utilizando uma solução de HCl 1,0 mol L-1. Foi realizada inicialmente, uma tentativa de analisar o CAPB diluindo-o diretamente em água, porém, mesmo após tentativas de pré-concentração on-line como o Stacking (plug de água antes da injeção da amostra) e injeção de amostra no modo eletrocinético, os subprodutos presentes na amostra, interferiram, prejudicando a detectabilidade do método. Então, foi proposta uma alternativa de preparo de amostra por meio da destilação por arraste de vapor, que permitiu isolar o DMAPA de sua matriz, diminuindo o limite de detecção (LOD) e LOQ do método proposto. Posteriormente foi construída uma curva analítica processada (em CAPB) e o método proposto apresentou boa precisão (%CV < 5) e linearidade (R2=0,9955 faixa linear de 2,0 a 20 mg kg-1), com LOD e LOQ de 0,03 mg kg-1 e 0,1 mg kg-1, respectivamente. O método proposto nesta dissertação alcançou o objetivo desejado, uma vez que apresentou um LOQ para o DMAPA abaixo da especificação exigida pelos clientes no produto final, e significativamente mais rápido do que o método atualmente utilizado pela Clariant S/A.
The amphoteric surfactant cocoamidopropyl betaine (CAPB) is widely used in pharmaceuticals and cosmetics industries, and is considered an essential input for the formulation of liquid soaps, shampoos and facial cleansing gels. Its synthesis is based on the reaction between fatty acid and coconut dimethylaminopropylamine (DMAPA) and subsequent reaction with monocloroacetic acid (MCA). The excess of DMAPA, regarded as an impurity, needs to be monitored because of its skin, eyes and mucous membranes irritability and in some cases, it causes dermatitis. Currently, the method adopted by Clariant S/A Industry for the determination of this substance is based on high performance liquid chromatography (HPLC). However, this method has a high analysis time and solvent consumption, compromising the productivity because of the inactive reactors which cannot be operated without the results of DMAPA analysis. There is a growing demand in the cosmetics industry to use methodologies which use time and cost criteria for determination of impurities to ensure the end products quality. Thus, in order to increase efficiency in the production process, this paper aims to propose a fast and reliable method for capillary electrophoresis to determine the DMAPA content during production (process control) and in the end product (CAPB surfactant). In this study, we addressed several sample preparation techniques and instrumental conditions to achieve an LOQ (limit of quantification) 10 mg kg-1 (specification required by the customer in the final product). The DMAPA was analyzed as cation, using a running buffer with imidazole and HIBA (a-hydroxybutyric acid), both with concentration of 0.01 mol L-1, and pH adjusted to 4.0 using a solution of HCl 1.0 mol L-1. First, CAPB was diluted directly in water. However, even after online preconcentration as Stacking (water plug before sample injection) and sample injection using the electrokinetic mode, the by-products present in the sample interfered in the method detectability. Thus, it was proposed an alternative sample preparation by steam distillation, allowing the isolation of the DMAPA from its matrix, lowering the limit of detection (LOD) and LOQ. Subsequently a processed calibration curve was constructed (in CAPB) and the proposed had good precision (CV% <5) and linearity (R2 = 0.9955, linear range from 2.0 to 20 mg kg-1), with LOD and LOQ of 0.03 mg kg-1 and 0.1 mg kg-1, respectively. The developed method in this thesis has achieved its purpose, since it presented an LOQ for the DMAPA below the required specification by customers in the final product, and significantly faster than the method currently used by Clariant S/A.

Methods were developed for the determination of methylmercury in natural waters and sediments based on steam distillation and aqueous phase ethylation followed by gas chromatography-atomic fluorescence spectrometry. The methods were shown to be free from measurable artefactual methylation of inorganic mercury and offered improved sample throughput over existing methods. Improvements were made to existing methods for the determination of total mercury in biota, sediments and natural waters and dissolved mercury species in natural waters. These methods were applied to the study of mercury cycling in two remote field sites. The cycling of mercury species was studied in Lake Murray in Western Province, Papua New Guinea, which has been historically noted as a region of high mercury concentrations in fish. Concentrations of methylmercury and total mercury in the water column were found to be variable and consistent with non-contaminated lake systems. Concentrations of methylmercury and total mercury in the sediments were also found to be low, except for in the south of the lake, which was influenced by an intermittent supply of water and sediments with elevated mercury concentrations from the Strickland River. Methylmercury concentrations in the sediments were generally higher in the backwater areas due to littoral processes. The low concentrations of methylmercury in the sediments and waters were inconsistent with other systems previously studied in the northern hemisphere, showing a link between high mercury concentrations in fish and high concentrations of methylmercury in waters or sediments. Therefore, the biota of Lake Murray were studied in order to account for the differences between this and other systems. A study was conducted of the stable isotope ratios of carbon and nitrogen in biota from Lake Murray to elucidate key food-web interactions. This study revealed that the dominant carbon source for fish in the lake is plankton, although algae and macrophytes may also be involved in the food-web. The methylmercury bioaccumulation factors between trophic levels were similar to those measured in temperate systems of the northern hemisphere. The high concentrations of methylmercury, observed in piscivorous fish, were shown to be a consequence of the complex food-web and the number of trophic levels in the food-chains. The cycling of mercury species was studied in Lake Gordon and Lake Pedder in southwest Tasmania, which has recently been identified as being in a region of high mercury concentrations in trout and eels. The concentrations of total mercury were found to be reasonably uniform in the waters of both lakes, spatially and temporally. The concentrations of methylmercury in the waters were seasonally variable, and were consistently lower in Lake Pedder than in Lake Gordon. Dilution of methylmercury concentrations by precipitation direct to the lake surface, probably accounts for the most of the difference in methylmercury concentrations between the lakes. Owing to the long residence time of water in Lake Gordon, this reservoir mixes inputs of water with varying methylmercury concentrations. Concentrations of total mercury and methylmercury in submerged soils were low and depth profiles of mercury species in the water column did not show evidence of a gradient of mercury concentrations due to releases from the sediments. The concentrations of methylmercury observed in the water column are consistent with the concentrations observed in the fish. A budget of the mercury inputs and outputs to Lake Gordon showed that in-lake processes and sources in the catchment areas both contributed significantly to the concentrations of methylmercury in the lake. The methylation of mercury in Lake Gordon appeared to mainly occur in the surface waters (< 10 m) and was not consistent with processes leading to the methylation of mercury at the oxic/anoxic boundary observed in seepage lakes in Wisconsin. The concentrations of total mercury and methylmercury in bogs in the catchment areas of Lakes Gordon and Pedder, were high and governed by the concentration of organic matter in the sediments. The processes involved in the supply of mercury species from the Lake Gordon and Lake Pedder catchments appear to be similar to those in drainage lakes in the temperate and boreal regions of the northern hemisphere. The formation of the Lake Gordon and Lake Pedder reservoirs appears to have had little impact on the mean annual concentrations of methylmercury released to the downstream environment.

Orientador: Maria Angela de Almeida Meireles
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos
Made available in DSpace on 2018-08-16T15:05:33Z (GMT). No. of bitstreams: 1 NavarroDiaz_HelmutJoel_M.pdf: 20602791 bytes, checksum: 810d1333271b6db64857c64c3c2a7904 (MD5) Previous issue date: 2010
Resumo: O resumo poderá ser visualizado no texto completo da tese digital
Abstract: The abstract is available with the full electronic document
Mestrado
Mestre em Engenharia de Alimentos

Orientador: Maria Angela de Almeida Meireles
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos
Made available in DSpace on 2018-08-09T21:18:11Z (GMT). No. of bitstreams: 1 Leal_PatriciaFranco_D.pdf: 2381293 bytes, checksum: 5131ad6a5dbd2eb071d1516e4f5d09fc (MD5) Previous issue date: 2008
Resumo: Este estudo teve por objetivo comparar o custo de manufatura (COM) de extratos vegetais e óleos voláteis de plantas aromáticas, condimentares e medicinais nativas ou adaptáveis ao cultivo brasileiro obtidos por processos de extração considerados limpos e que não agridem o meio ambiente. Foi realizado o estudo técnico-econômico do processo de extração com fluido supercrítico (SFE) e destilação por arraste a vapor (SD) para obtenção de extratos vegetais e óleos voláteis. A metodologia de estimativa de custo de manufatura utilizada neste estudo resulta em COM classe 4 ou 5, sendo uma estimativa preliminar para a decisão de prosseguimento ou a interrupção do projeto. As estimativas dos custos de manufatura dos extratos foram realizadas através das curvas globais de extração (OEC) dos sistemas determinadas experimentalmente neste trabalho (alecrim + vapor, camomila + vapor, erva-doce + vapor, erva-baleeira + vapor, erva-baleeira + CO2, canelinha + CO2) e também através das OECs da literatura (alecrim + vapor, alecrim + CO2, erva-doce + vapor, erva-doce + CO2,, gengibre + CO2, camomila + CO2, pimenta-do-reino + vapor, pimenta-do-reino + CO2, funcho + CO2,). As curvas globais de extração foram ajustadas a um spline contendo duas ou 3 retas: a primeira reta descreve a taxa de transferência de massa no período de taxa de extração constante (CER), a segunda reta descreve a taxa de transferência de massa no período de taxa de extração decrescente (FER) e a terceira reta descreve a taxa de transferência de massa no período controlado pela difusão (DC). Para o scale-up assumiu-se que o rendimento de extração e o tempo do processo para o equipamento em escala industrial são linearmente correlacionados aos parâmetros da escala laboratorial quando é mantida constante a razão entre a massa de solvente e a massa de alimentação. Os COMs para os extratos obtidos por SD e SFE foram estimados durante todo o processo de extração para tempos pré-selecionados ao longo das OECs. Para os extratos obtidos por SFE, o COM também foi estimado para dois tempos de processo préselecionados: (i) o tempo de ciclo correspondente ao período CER e denotado por tCER e (ii) tempo de ciclo correspondente à intercepção das retas que representam os períodos CER e DC e denotado por tCER2. O parâmetro tCER é amplamente proposto pela literatura e como uma boa aproximação para o tempo de ciclo do processo SFE, tendo em vista que aproximadamente 70% do leito de extração é esgotado nesta etapa. Para as OECs ajustadas a um spline linear contendo três retas o tempo de ciclo foi selecionado como tCER2. Através do estudo de simulação da etapa de separação extrato/solvente realizado para os sistemas funcho + CO2 e canelinha + CO2 foi possível observar que a condição de operação desta etapa tem grande influência na composição do extrato final. A pressão de operação do tanque flash igual a 40 bar foi considerada uma boa alternativa, pois tanto a perda de CO2 na corrente de saída de extrato quanto a perda de extrato na corrente de saída de solvente foram mínimas. O estudo da etapa de separação é uma área promissora e ainda pouco explorada frente à etapa de extração. Foi avaliado o impacto do custo fixo de investimento, custo de matéria-prima, custo de utilidades, custo de mão-de-obra e custo de tratamento de resíduos sobre o COM. Este estudo foi importante, pois quebrou o paradigma de que o custo fixo de investimento seria o fator de maior impacto no COM dos extratos produzidos por SFE. O custo de matéria-prima predominou na composição do COM dos extratos da grande maioria das matrizes vegetais obtidas por SFE e SD. A SFE é um processo promissor e já existem inúmeras unidades industriais operando na China, França, Alemanha, etc. A estimativa preliminar dos custos de manufatura dos extratos de erva-baleeira, alecrim, camomila, erva-doce e pimenta-do-reino obtidos por SFE e SD foram: US$ 914,00/kg e US$ 10.350,00/kg, US$ 214,00/kg e US$ 369,00/kg, US$ 277,00/kg e US$ 2.798,00/kg, US$ 216,00/kg e US$ 272,00/kg, US$ 198,00/kg e US$ 232,00/kg, respectivamente. Estes custos foram comparados ao preço de venda de similares produzidos no Brasil e/ou exterior. A produtividade anual para cada processo foi confrontada
Abstract: This study had the objective to compare the cost of manufacturing (COM) of vegetable extracts and volatile oils of aromatic, condimental and medicinal plants, natives or adaptable to cultivation in Brazil, obtained by extraction processes that are clean and harmless to the environment. A technical-economical study on supercritical fluid extraction (SFE) and steam distillation (SD) for obtaining of vegetable extracts and volatile oils was done. The methodology to estimate the cost of manufacturing used on this study produces estimation classified as COM class 4 or 5, being a preliminary estimation used in the decision of go or not go of the project. The cost of manufacturing estimations were done using information from the overall extraction curves (OEC) experimentally determined in this study (rosemary + steam, chamomile + steam, anise + steam, C. verbenacea + steam, C. verbenacea + CO2, C. zehntneri + CO2) and information obtained from literature for OECs (rosemary + steam, rosemary + CO2, anise + steam, anise + CO2, ginger + CO2, chamomile + CO2, black pepper + steam, black pepper + CO2, fennel + CO2). The overall extraction curves were fitted to a spline containing two or three lines: the first line describes the mass transfer rate for the constant extraction rate period (CER), the second line describes the falling extraction rate period (FER), and the third line describes the diffusion controlled rate period (DC). The scale-up procedure assumed that both the global yield and the time of processing of the industrial scale are linearly correlated to laboratory scale ones as long as the ratio of the solvent mass to the raw material mass is kept constant. The COMs of the extracts obtained by SD and SFE were estimated from beginning to end of the process at specified time intervals along the OECs. For the SFE process the COM was also estimated for two preselected times of process: (i) a time of cycle corresponding to CER period and denoted as tCER, and (ii) a time of cycle corresponding to the intercept of the CER and DC lines denoted in this study as tCER2. The tCER parameter is widespread in literature as being a good estimative for the time of processing for the SFE since approximately 70% of extraction bed is exhausted along this period. For the OECs adjusted to a linear spline containing three lines the time of cycle was chosen as tCER2. The simulation of the separation extract/solvent done for fennel + CO2 and C. zehntneri + CO2 system, showed that the operation conditions of this stage have great influence on the final composition of the extract. The operation pressure of 40 bar in the flash tank was considered as a good choice, since a minimum loss of CO2 (in the extract exit stream) and the extract loss (in the CO2 exit stream) were estimated. The study of the separation stage is a promising area, and still little explored when compared to the extraction stage. The impact of the fixed cost of investment, raw material cost, utilities cost, operational-labor cost and waste treatment cost on the COM were evaluated. This study was important since it broke the paradigm that the fixed cost of investment would be the factor of major impact on the COM of the extracts produced by SFE. The raw material cost was predominant on the composition of the COM of the extracts from most vegetable matrices obtained by SFE and SD. SFE is a promising process, and there already are many industrial units operating in China, France, Germany, etc. The preliminary estimative of the manufacturing costs of the extracts of C. verbenacea, rosemary, chamomile, anise and black pepper obtained by SFE and SD were: US$ 914.00/kg and US$ 10,350.00/kg, US$ 214.00/kg and US$ 369.00/kg, US$ 277.00/kg and US$ 2,798.00/kg, US$ 216.00/kg and US$ 272.00/kg, US$ 198.00/kg and US$ 232.00/kg, respectively. These costs were compared to the selling prices of similar products produced in Brazil and/or abroad. The annual productivities of each process were confronted.
Doutorado
Engenharia de Alimentos
Doutor em Engenharia de Alimentos

Thesis (MScEng (Process Engineering))--Stellenbosch University, 2010.
ENGLISH ABSTRACT: Recently, improved technologies have been developed for the biobutanol fermentation process: higher butanol concentrations and productivities are achieved during fermentation, and separation and purification techniques are less energy intensive. This may result in an economically viable process when compared to the petrochemical pathway for butanol production. The objective of this study is to develop process models to compare different possible process designs for biobutanol production from sugarcane molasses. Some of the best improved strains, which include Clostridium acetobutylicum PCSIR-10 and Clostridium beijerinckii BA101, produce total solvent concentrations of up to 24 g/L. Among the novel technologies for fermentation and downstream processing, fedbatch fermentation with in situ product recovery by gas-stripping, followed by either liquid-liquid extraction or adsorption, appears to be the most promising techniques for current industrial application. Incorporating these technologies into a biorefinery concept will contribute toward the development of an economically viable process. In this study three process routes are developed. The first two process routes incorporate well established industrial technologies: Process Route 1 consist of batch fermentation and steam stripping distillation, while in Process Route 2, some of the distillation columns is replaced with a liquid-liquid extraction column. The third process route incorporates fed-batch fermentation and gas-stripping, an unproven technology on industrial scale. Process modelling in ASPEN PLUS® and economic analyses in ASPEN Icarus® are performed to determine the economic feasibility of these biobutanol production process designs. Process Route 3 proved to be the only profitable design in current economic conditions. For the latter process, the first order estimate of the total project capital cost is $187 345 000.00 (IRR: 35.96%). Improved fermentation strains currently available are not sufficient to attain a profitable process design without implementation of advanced processing techniques. Gas stripping is shown to be the single most effective process step (of those evaluated in this study) which can be employed on an industrial scale to improve process economics of biobutanol production.
AFRIKAANSE OPSOMMING: Onlangse verbeteringe in die tegnologie vir die vervaardiging van butanol via die fermentasie roete het tot gevolg dat: hoër butanol konsentrasies en produktiwiteit verkry kan word tydens die fermentasie proses, en energie verbruik tydens skeiding-en suiweringsprosesse laer is. Hierdie verbeteringe kan daartoe lei dat biobutanol op ʼn ekonomiese vlak kan kompeteer met die petrochemiese vervaardigings proses vir butanol. Die doelwit van die studie is om proses modelle te ontwikkel waarmee verskillende proses ontwerpe vir die vervaardiging van biobutanol vanaf suikerriet melasse vergelyk kan word. Verbeterde fermentasie organismes, wat insluit Clostridium acetobutylicum PCSIR-10 en Clostridium beijerinckii BA101, het die vermoë om ABE konsentrasies so hoog as 24 g/L te produseer. Wat nuwe tegnologie vir fermentasie en skeidingprosesse behels, wil dit voorkom of wisselvoer fermentasie met gelyktydige verwydering van produkte deur gasstroping, gevolg deur of vloeistof-vloeistof ekstraksie of adsorpsie, van die mees belowende tegnieke is om tans in die nywerheid te implementeer. Deur hierdie tegnologie in ʼn bioraffinadery konsep te inkorporeer sal bydra tot die ontwikkeling van ʼn ekonomies lewensvatbare proses. Drie prosesserings roetes word in die studie ontwikkel. Die eerste twee maak gebruik van goed gevestigde industriële tegnologie: Proses Roete 1 implementeer enkellading fermentasie en stoom stroping distillasie, terwyl in Proses Roete 2 van die distilasiekolomme vervang word met ʼn vloeistof-vloeistof ekstraksiekolom. Die derde proses roete maak gebruik van wisselvoer fermentasie met gelyktydige verwydering van produkte deur gas stroping. Die tegnologie is nog nie in die nywerheid bewys of gevestig nie. Om die ekonomiese uitvoerbaarheid van die proses ontwerpe te bepaal word proses modellering uitgevoer in ASPEN PLUS® en ekonomiese analises in ASPEN Icarus® gedoen. Proses Roete 3 is die enigste ontwerp wat winsgewend is in huidige ekonomiese toestande. Die eerste orde koste beraming van die laasgenoemde projek se totale kapitale koste is $187 345 000.00 (opbrengskoers: 35.96%). Die verbeterde fermentasie organismes wat tans beskikbaar is, is nie voldoende om ʼn proses winsgewend te maak nie; gevorderde proses tegnologie moet geïmplementeer word. Gasstroping is bewys as die mees effektiewe proses stap (getoets in die studie) wat op industriële skaal geïmplementeer kan word om die winsgewendheid van die biobutanol proses te verbeter.
Centre for Renewable and Sustainable Energy Studies

Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2017-10-25T23:42:57Z No. of bitstreams: 1 Daniela_C_O_Bueno_2016.pdf: 2802809 bytes, checksum: ff40fea77fdb8dbe45d71a56b942127c (MD5)
Made available in DSpace on 2017-10-25T23:42:57Z (GMT). No. of bitstreams: 1 Daniela_C_O_Bueno_2016.pdf: 2802809 bytes, checksum: ff40fea77fdb8dbe45d71a56b942127c (MD5) Previous issue date: 2016-02-29
The trees are part of our daily life: in urban areas, as shadow production elements, landscaping, water infiltration, reduced thermal sensation, attenuation of noise, breaking wind, oxygen release / absorption of pollutants and as micro habitats for wildlife; and in rural areas, some cultures such as pine are distinguished primarily as energy sources (wood) in the industrial sector. In all cases the common characteristic is the generation of waste is the pruning process and / or processing / production of wood processing. In most cases these residues are intended to landfills, discarding the potential use as raw material for the production of essential oils. On that basis, the aim of this study was to develop a technology for essential oil extraction using an alternative method based on the incremental innovation. Therefore, the methodology included six stages: 1) characterization of the raw material; 2) Technology prospecting; 3) alternative technology proposition; 4) Prototyping through design, construction and assembly components; 5) Operational tests in real operating condition; and 6) the requirements of novelty evaluation, inventive step, sufficiency descriptive and industrial application for intellectual property protection. The result of the work was a technological product, pilot-scale production of essential oil residues from tree pruning and firewood production endowed simultaneously generating steam and carbon dioxide. The resulting equipment introduced innovative features and was the object of protection with the National Institute of Industrial Property (INPI) under No. 2015 032186-0 BR 20 with the following attributes: possibility of operation of the modular systems either independently or together, possibility of continuous operation or in batch, using as extracting fluid vapor and / or carbon dioxide and versatility in size and enforcement capacity in various materials that have, in their composition, essential oils. The work also had as a development technology for use in saunas which was also object patent (Patent No. BR 20 2015 032185-1). The project in question is inserted in the area of technological innovation and in its early stages prioritized the development of technology and in the second phase should be complemented with the optimization of the operational part. Thus, it contributes to environmental technology for the recovery of waste from pruning and / or industrial wood processing.
As árvores fazem parte do nosso cotidiano: na área urbana, como elementos de produção de sombra, paisagismo, infiltração da água, redução da sensação térmica, atenuação da poluição sonora, quebra de ventos, liberação de oxigênio/absorção de poluentes e como micro hábitats para a fauna; e na área rural, algumas culturas como o pinus primam essencialmente como fontes energéticas (lenha) do setor industrial. Em todos os casos a característica comum é a geração de resíduos, seja do processo de poda e/ou do processamento/beneficiamento na produção de lenha. Na maioria dos casos esses resíduos são destinados aos aterros sanitários, descartando-se o potencial do aproveitamento, como matéria prima para a produção de óleos essenciais. Partindo deste pressuposto, o objetivo deste trabalho foi desenvolver uma tecnologia para extração de óleo essencial utilizando um método alternativo com base da inovação incremental. Para tanto, a metodologia contemplou seis etapas: 1) Caracterização da matéria prima; 2) Prospecção tecnológica; 3) Proposição de tecnologia alternativa; 4) Prototipagem por meio de projeto, construção e montagem de componentes; 5) Testes operacionais na condição real de operação; e 6) Avaliação dos requisitos de novidade, atividade inventiva, suficiência descritiva e aplicação industrial para proteção intelectual. O resultado do trabalho foi um produto tecnológico, em escala piloto, para produção de óleo essencial de resíduos da poda de árvores e da produção de lenha dotado de gerador simultâneo de vapor e gás carbônico. O equipamento resultante apresentou características inovadoras e foi objeto de proteção junto ao Instituto Nacional de Propriedade Industrial (INPI) sob o Nº BR 20 2015 032186-0 com os seguintes atributos: possibilidade de operação dos seus sistemas modulares de maneira independente ou em conjunto, possibilidade de operação de forma contínua ou em batelada, utilizando como fluído extrator o vapor e/ou gás carbônico e versatilidade no seu tamanho e capacidade de aplicação em diversos materiais que possuem, na sua composição, óleos essenciais. O trabalho teve também como desdobramento uma tecnologia para utilização em saunas o qual também foi objeto de patenteamento (Patente Nº BR 20 2015 032185-1). O projeto em questão se encontra inserido na área de inovação tecnológica e na sua fase inicial priorizou o desenvolvimento da tecnologia e na segunda fase deve ser complementado com a otimização da parte operacional. Desta forma, contribui-se com a tecnologia ambiental para o aproveitamento dos resíduos de podas e/ou do beneficiamento de lenha industrial.

Les régions de Midi-Pyrénées (France) et de Chongqing (Chine) sont riches en plantes aromatiques et médicinales dites oubliées (ou médiévales). Afin de valoriser pleinement les différentes bio-molécules extractibles de ces plantes, le concept de MAP-raffinerie a été créé et appliqué à une sélection de plantes issues de ces deux régions. Plusieurs technologies d’extraction utilisant l’eau comme solvant vert (hydrodistillation, distillation à la vapeur et extraction par eau sub-critique) ont ainsi été employées et leur impact tant sur la composition des huiles essentielles que sur la récupération des molécules anti-oxydantes a été évalué. Dans un premier temps, une liste de plantes aromatiques et médicinales oubliées, voire sous-utilisées dans les deux régions a été établie selon des règles de sélection prédéfinies. Six plantes modèles de la région de Midi-Pyrénées (Tussilago farfara L., Calendula arvensis L., Robinia pseudoacacia L., Geranium robertianum L., Cytisus scoparius L. et Spartium junceum L.) et trois plantes de la région de Chongqing (Tussilago farfara L., Citrus aurantium L. et Saussurea costus) ont finalement été retenues. Puis, le concept de MAP-raffinerie a été appliqué à ces plantes afin d’étudier leur possible valorisation globale. L’étude des compositions chimiques des extraits volatils des racines de Tussilago farfara L. et de Calendula arvensis L., ainsi que des boutons de fleurs de Spartium junceum L. a été réalisée par GC et GC-MS pour la première fois. Les principaux composés chimiques dans l’extrait volatil de racines de Tussilago farfara L. étaient des hydrocarbures sesquiterpéniques et des composés aliphatiques tandis que les principaux composés chimiques dans l’extrait volatil de racines de Calendula arvensis L. étaient des sesquiterpènes oxygénés, des monoterpènes oxygénés et des diterpènes oxygénés. L’extrait volatil de boutons de fleurs de Spartium junceum L. était principalement composé de composés aliphatiques. Par ailleurs, les résultats de l’évaluation des capacités anti-oxydantes des extraits (par les tests DPPH, ABTS, FRAP, ORAC et Folin-Ciocalteu) ont montrés que plusieurs plantes comme Cytisus scoparius L., Tussilago farfara L., Citrus aurantium L. ou Robinia pseudoacacia L. pourraient être des sources potentielles d’anti-oxydants naturels. D’un point de vue technologique, les comparaisons de l’utilisation de l’hydrodistillation (HD), de la distillation à la vapeur (SD) et de l’extraction par eau sub-critique (SWE) ont montrées que si la HD et la SD ont des effets limités sur la composition des huiles essentielles, la HD semble être une méthode plus efficace pour la récupération des composés anti-oxydants à partir des résidus de distillation que la SD tandis que la SWE s’avère être une technologie prometteuse pour l’extraction directe de ces molécules à partir des plantes. Si la composition minérale de l’eau lors de l’hydrodistillation n’a que des effets très limités sur les rendements d’extraction, les teneurs en ions calcium et bicarbonate des eaux ont par contre des effets décroissants significatifs sur la capacité anti-oxydante et sur la teneur phénolique totale des extraits aqueux et méthanoliques. Au vue de ces résultats, un concept amélioré de MAP-raffinerie a été développé en intégrant une extraction à l’eau sub-critique pour l’extraction des composés anti-oxydants des résidus d’extraction primaire. Selon ce nouveau concept, cinq extraits peuvent être obtenus à partir des matières végétales: un extrait volatil, un extrait aqueux, un extrait méthanolique, un extrait à l’eau sub-critique et in fine un résidu solide. Les premiers résultats ont montrés que la "MAP-raffinerie améliorée" augmente de manière significative la récupération des antioxydants par rapport à la MAP-raffinerie originale et permet d’envisager une valorisation plus facile du résidu solide en agro-matériaux du fait de sa faible teneur en eau résiduelle
In both Midi-Pyrénées region (France) and Chongqing region (China), there are rich and underutilized medicinal and aromatic plants (MAP). Aiming at fully exploiting different molecules in these plants, the concept of MAP-refinery was developed and applied to several underutilized medicinal and aromatic plants in these two regions. Several water-based green extraction technologies of natural products (e.g. hydrodistillation, steam distillation and subcritical water extraction) were also investigated to look at their effects on essential oil composition and antioxidants recovery from selected plants. Firstly, lists of forgotten or underutilized medicinal and aromatic plants in both regions were established according to the rules of selection. From the lists, six plants in the Midi-Pyrénées region (Tussilago farfara L., Calendula arvensis L., Robinia pseudoacacia L., Geranium robertianum L., Cytisus scoparius L. and Spartium junceum L.) and three plants in the Chongqing region (Tussilago farfara L., Citrum aurantium L. and Saussurea costus) were finally selected for investigations. Then the MAP-refinery was applied to the selected plants in two regions in order to realise their global valorisation. Volatile extracts composition in the roots of Tussilago farfara L. and Calendula arvensis L., as well as flower buds of Spartium junceum L. were firstly investigated. The main chemical compounds in volatile extract from Tussilago farfara L. roots were sesquiterpene hydrocarbons and aliphatic compounds while main chemical compounds in volatile extract from Calendula arvensis L. roots were oxygenated sesquiterpenes, oxygenated monoterpenes and oxygenated diterpenes. The volatile extract from flower buds of Spartium junceum L. was mainly composed of aliphatic compounds. Antioxidant capacity evaluation results (by DPPH, ABTS, FRAC, ORAC and Folin-Ciocalteu tests) showed that several plant samples like Cytisus scoparius L., Tussilago farfara L., Citrum aurantium L. and Robinia pseudoacacia L. could be potential sources of natural antioxidants. Comparisons of hydrodistillation (HD), steam distillation (SD) and subcritical water extraction (SWE) showed that HD and SD had limited effects on essential oil composition but HD, SD and SWE had significant impacts on the recovery of antioxidants. Hydrodistillation seemed to be a better method for recovery of antioxidant compounds from residues of distillation than steam distillation. However, SWE appeared to be a more efficient method for direct extraction of antioxidant molecules (or phenolic compounds) from plants. In the hydrodistillation process, mineral contents in water were found to have very limited effects on yields of extracts but calcium and bicarbonate ions, had significant decreasing effects on antioxidant capacity and total phenolic content of both aqueous and methanolic extracts. Finally, an improved MAP-refinery was developed. Subcritical water was used for further extraction of antioxidant compounds from residues in original MAP-refinery. In this way, five parts could be obtained from plant materials: volatile extract, aqueous extract, methanolic extract, subcritical water extract and the final residue. The results showed that the improved MAP-refinery significantly increased the recovery of antioxidants compared with original MAP-refinery. This promising process will also allow a better valorisation of the final solid residue due to the lower content of residual water

[EN] Anaerobic digestion is a sustainable and technically sound way to valorise citrus waste if the inhibitory effect of the citrus essential oil (CEO) is controlled. Several strategies have been proposed to overcome these difficulties: keeping the organic loading rate (OLR) in low values to avoid excess dosage of inhibitor, supplementing the citrus waste with nutrient and buffering solutions or pre-treating the citrus waste in order to reduce the CEO concentration, either by recovery or by degradation of the CEO. Nevertheless, although some of them have been proven successful in recovering/degrading the CEO, none of them has been applied at full scale operation. The main objective of this thesis is to study the effect of the limonene (the main component of CEO) on the anaerobic digestion of citrus waste and to evaluate different strategies to improve this process. In a first approach to the problem, the effect and dynamics of the limonene in the anaerobic digestion process is studied in batch mode. The biochemical methane potential of several citrus waste types was assessed. The inhibitory concentration of limonene for the anaerobic digestion process was estimated also, observing a certain adaptation degree. Different strategies to avoid inhibition of the anaerobic digestion by limonene were studied in batch mode, namely biological treatment by fungi of the Penicillium genus, steam distillation and ethanol extraction. All treatments decreased the limonene concentration in the orange peel, with different efficiencies. Methane potential and production rate in the batch anaerobic digestion of the pretreated orange peel were not affected by the biological treatment, but an increase was observed after steam distillation and also after ethanol extraction. This effect was attributed to the removal of minority compounds of the CEO. Energy balance was negative for steam distillation and positive for the other two tested strategies. Continuous anaerobic co-digestion experiments of orange and mandarin peel with chicken and pig manure allowed observing the importance of the limonene dosage on the inhibitory effect. Systemic inhibition was observed in the mixture with higher limonene concentration, with symptoms of inhibition on methanogenesis, protein hydrolysis pathway, sulphate reduction and acetogenesis. The degradation of the limonene produced inhibitory compounds as well, causing persistent inhibition effects even after almost complete limonene degradation. Continuous anaerobic co-digestion of pretreated citrus waste with cow manure allowed for stable processes when the pretreatment was able to remove the limonene with high efficiency and without producing other inhibitory compounds (such as ¿-terpineol in the biological treatment). Thus, the pretreatments allowing for better results in terms of process stability were mechanical removal of the flavedo and ethanol extraction of the limonene. The anaerobic digestion is able to degrade the limonene, but its by-products can be even more inhibitory than the limonene itself. Therefore, it is concluded that to apply CEO recovery strategies before anaerobic digestion is recommended, since these could possibly the valorization of CEO as added value product and to increase biogas production.
[ES] La digestión anaerobia es una vía sostenible y técnicamente viable para valorizar los residuos cítricos si se controla el efecto inhibidor del aceite esencial cítrico (AEC). Se han propuesto varias estrategias para superar esta dificultad: mantener la velocidad de carga orgánica (VCO) en valores bajos para evitar dosis excesivas del inhibidor, suplementar el residuo cítrico con soluciones de nutrientes y tampón o pretratar el residuo cítrico para reducir la concentración de AEC, ya sea por recuperación o degradación del mismo. Sin embargo, aunque algunas de ellas han sido exitosas para recuperar o degradar el AEC, ninguna ha sido llevada a escala industrial. El objetivo principal de esta tesis ha sido estudiar el efecto del limoneno (el componente principal del AEC) en la digestión anaerobia de los residuos cítricos y evaluar diferentes estrategias para mejorar este proceso. En una primera aproximación al problema, se estudió el efecto y la dinámica del limoneno en la digestión anaerobia en discontinuo. Se evaluó el potencial bioquímico de metano de varios tipos de residuo cítrico y se estimó la concentración inhibitoria del limoneno para el proceso de digestión anaerobia, observando un cierto grado de adpatación. Se estudiaron diferentes estrategias para evitar la inhibición de la digestión anaerobia por limoneno en modo discontinuo: tratamiento biológico mediante hongos del género Penicillium, arrastre de vapor y extracción con etanol. Todos los tratamientos disminuyeron la concentración de limoneno en la piel de naranja, con diferentes eficiencias. El potencial de metano y la velocidad de producción en la digestión anaerobia discontinua de la piel de naranja pretratada no se vieron afectados por el tratamiento biológico, pero se observó un incremento tras el arrastre de vapor y la extracción con etanol. Este efecto se atribuyó a la extracción de compuestos minoritarios del AEC. El balance energético fue negativo para el arrastre de vapor y positivo para las otras dos estrategias. Los experimentos de co-digestión anaerobia en continuo de piel de naranja y mandarina con gallinaza y purín porcino permitieron observar la importancia de la dosis de limoneno sobre el efecto inhibitorio. Se observó inhibición sistémica en la mezcla con mayor concentración de limoneno. La degradación del limoneno produjo a su vez compuestos inhibitorios, con lo que el efecto inhibitorio persistió incluso tras la completa degradación del limoneno. La co-digestión anaerobia en continuo de residuo cítrico pretratado y estiércol de vacuno permitió tener procesos estables cuando el pretratamiento era capaz de eliminar el limoneno con alta eficiencia y sin producir otros compuestos inhibitorios (como ¿-terpineol en el caso del tratamiento biológico). Así, la eliminación mecánica del flavedo y la extracción del limoneno con etanol fueron los pretratamientos que dieron mejor resultado en términos de estabilidad del proceso. La digestión anaerobia es capaz de degradar el limoneno, pero sus subproductos pueden ser aún más inhibitorios que el propio limoneno. Por ello, se concluye que son recomendables los pretratamientos de recuperación de AEC, ya que permiten su valorización como producto de valor añadido y, a la vez, incrementar la producción de biogás mediante digestión anaerobia.
[CAT] La digestió anaeròbia és una via sostenible i tècnicament viable per valoritzar els residus cítrics si es controla l'efecte inhibitori de l'oli essencial cítric (OEC). S'han proposat diverses estratègies per tal de superar aquesta dificultat: mantenir la velocitat de càrrega orgànica (VCO) en valors baixos per a evitar dosis excessives de l'inhibidor, suplementar el residu cítric amb solucions de nutrients i tamponants o pretratar el residu cítric per a reduir la concentració d'OEC, ja siga per recuperació o per degradació del mateix. Tanmateix, encara que algunes d'elles han estat exitoses per recuperar o degradar l'OEC, cap ha estat escalada a nivel industrial. L'objectiu principal d'aquesta tesi ha estat estudiar l'efecte del limonè (el component principal de l'OEC) en la digestió anaeròbia dels residus cítrics i avaluar diferents estratègies per a millorar aquest procés. En una primera aproximació al problema, es va estudiar l'efecte i la dinàmica del limonè a la digestió anaeròbia en discontinu. Es va avaluar el potencial bioquímic de metà de diferents tipus de residu cítric i es va estimar la concentració inhibitòria del limonè per al procés de digestió anaeròbia, observant-se un cert grau d'adaptació. S'estudiaren diferents estratègies per a evitar la inhibició de la digestió anaeròbia per limonè en modus discontinu: tractament biològic amb fongs del gènere Penicillium, destil·lació amb vapor i extracció amb etanol. Tots els tractaments reduiren la concentració de limonè a la pell de taronja, però amb eficiències diferents. El pre-tractament biològic no va influir en el potencial de metà ni en la velocitat de producció de la digestió anaeròbia discontínua de la pell de taronja. En canvi, s'observà un increment d'ambdós paràmetres amb la destil·lació amb vapor i l'extracció amb etanol. Aquest efecte es va atribuir a l'extracció de components minoritaris de l'OEC. El balanç energètic va ser negatiu per a la destil·lació amb vapor i positiu per a les altres dues estratègies. Els experiments de co-digestió anaeròbia en continu de pell de taronja i mandarina, amb gallinassa i purins de porc varen permetre observar la importància de la dosi de limonè sobre l'efecte inhibitori. Es va observar inhibició sistèmica a la mescla amb major concentració de limonè. La degradació del limonè va produir inhibidors, de manera que l'efecte inhibitori va persistir fins i tot després de la completa degradació del limonè. La co-digestió anaeròbia en continu de residu cítric pretractat i fem de boví va permetre tenir processos estables quan el pretractament era capaç d'eliminar el limonè amb alta eficiència i sense produir altres molècules inhibitòries (com α-terpineol en el cas del tractament biològic). Així, l'eliminació mecànica de l'epicarpi i l'extracció del limonè amb etanol foren els pretractaments que donaren millor resultat en termes d'estabilitat del procés. La digestió anaeròbia és capaç de degradar el limonè, però els seus subproductes poden ser encara més inhibitoris que el propi limonè. Per això, es conclou que son recomanables els pretractaments de recuperació de OEC, ja que permenten la seva valorització com productes de valor afegit i, a la vegada, incrementar la producció de biogàs mitjançant digestió anaeròbia.
Ruiz Fuertes, B. (2015). Effect of limonene on anaerobic digestion of citrus waste and pretreatments for its improvement [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58769
TESIS

碩士
國立聯合大學
化學工程學系碩士班
104
Citronella is a plant with a special aroma and is belong to the Gramineae Cymbopogon species. It has a good antibacterial effect. It also can prevent mosquito bites and is widely apply in expelling mosquitoes, refining essential oils, etc. Entire citronella contains volatile oil and chemical compositions like citronellal, citral, limonene, myrcene, etc. However, the compositions and contents in the essential oils of Cymbopogon plants can be different depending on the source and the species. The citronella is extracted by steam distillation in the industry. The essential oil has a pale yellow color. Solvent extraction is one of the simplest separation methods. In this study, we found the optimal condition of solvent extraction of the citronella leave and their stem. Solvents used for extraction experiment are ethanol, acetone, and deionized water. The optimal extraction condition of the citronella is found by testing at different extraction times, types of solvent, solvent concentrations, and temperatures. The best extraction condition is 1 gram of citronella leave extracting in 60 wt.% ethanol (50 g) at 50℃. After 72 hours of extraction, a high extraction yield is obtained. The mean total extraction yield is 17.39 wt.%. The extraction yield from the citronella leave is better than from the stem. A pale yellow oil with unique odor is obtained in direct steam distillation. After 4 hours of extraction, the mean yield is 1.53 wt.% from the leaf and is 0.46 wt.% from the stem. The major compositions of commercial and homemade essential oil are analyzed by Fourier transform infrared spectroscopy (FTIR) and gas chromatograph (GC). The citronellal in the citronella oil is determined by the relative volumetric method. The citronellal in citronella oil made in our lab is 36.34 wt.% from the leaf and is 35.17 wt.% from the stem. The citral is determined by specific quantitative colorimetric method. The handmade leaf oil contains 25.38 wt.% of citral and the stem oil contains 13.12 wt.% of citral.

Nella seguente tesi è stato studiato e approfondito il processo di distillazione in corrente di vapore. La tesi è stata strutturata in quattro ricerche con l'obiettivo generale di ottimizzare e innovare il processo di distillazione in corrente di vapore. Sono stati affrontati due temi principali. Il primo ha riguardato "l'ottimizzazione del processo di distillazione in corrente di vapore" per minimizzare i consumi e massimizzare la resa dell'olio essenziale. Il secondo, l'innovazione del processo, intesa come possibilità di ampliarne il campo di applicazione. In dettaglio, il tema dell'ottimizzazione è stato affrontato da due studi, incentrati sull'indagine dei fattori che influenzano la resa dell'olio essenziale e sullo sviluppo dell'applicazione di un rivelatore a fotoionizzazione per il monitoraggio e il controllo dei diversi prodotti in diverse fasi del processo. Il tema dell' "innovazione di processo" è stato affrontato con due ulteriori studi su una possibile applicazione alternativa del processo. Nel dettaglio, sull'applicazione della distillazione in corrente di vapore come metodo sostenibile per il recupero di composti bioattivi ad alto valore aggiunto dagli scarti di alcune industrie agroalimentari. In the following thesis steam distillation process was studied and deepened. It was structured in four research with the overall aim to optimize and innovate the steam distillation process. Two main themes were addressed. The first concerned the optimization of the steam distillation process to minimize consumption and maximize the yield of the essential oil. The second, to innovate the process, understood as the possibility of expanding its field of application. In detail, the theme of optimization was addressed by two studies, focused on the investigation of the, of the factors affecting the yield of essential oil and, on the development the application of a photoionization detector for monitoring and controlling of the different products in several phases of the distillation process. The theme of “process innovation” was addressed with two further studies, on a possible alternative application of the process. In the detail, on the application of steam distillation as a sustainable method for the recovery of bioactive compounds with high added value from the waste of some agri-food industries.

碩士
中原大學
化學研究所
95
Pelargonium graveolens, a member of Geraniaceae family which has strong and specific scent. This plant contains essential oil which can be used for anti-inflammation or anti-microbial. Moreover, its fragrance can be used to repel insects and mosquitoes. In this study, the leaves and branches were gathered from fresh Pelargonium graveolens. After prepared processes, the slightly brown neutral essential oil was gathered by distillation and by using ether and hexane to partition before treatment with base to remove acidic compounds. Then, the essential oil mixture was separated and purified by column chromatography. The oil mixture was chromatographed into hydrocarbon and oxygenated fractions which were used to analyze its chemical components by using gas chromatography (GC) equipped with a flame ionization detector (FID), mass spectrometer detector (MSD), Fourier transform infrared spectrometer and nuclear magnetic resonance spectrometer (NMR). In the hydrocarbon fraction, some components were found. They go as follows. β-pinene、3-methylene-1,5,5-trimethylcyclohexene、α-phellandrene、o-cymene、sylvestrene、β-trans-ocimene、β-cis-ocimene、copaene、β-bourbonene、β-elemene、β-caryophyllene、α-guaiene、aristolene、α-gurjunene、α-caryophyllene、aromadendrene、germacrene D、isoledene、δ-selinene、α-muurolene、cadinene、τ-cadinene、δ-cadinene、β-maaliene were identified. There was first time to isolated aristolene from Pelargonium graveolens. In the oxygenated fraction, some components were found. They go as follows. linalool、menthone、geraniol、τ-eudesmol、geranic oxide、cineole、linalool oxide、rose oxide、myrcenol、isopulegol、α-cyclogeraniol、isomenthol、terpineol、β-citronellol、 β-citral、citronellyl formate、citronellyl propionate、geranyl propionate、citronellyl butanoate、geranyl、nerolidol isobutyrate、phenylethyl tiglate、agarospirol、τ-cadinol、geranyl tiglate were identified. By comparing the methods of extraction, 0.16% essential oil was gathered by indirect steam distillation while 0.14% essential oil was gathered by direct steam distillation from Pelargonium graveolens. Then, I compared the differences by tracing eight major components contents in oils which were gathered in two different ways. The findings go as follows. 1.Indirect steam distillation： linalool 5.79%、menthone 8.85%、β-citronellol 15.08%、geraniol 20.58%、aristolene 16.52%、germacrene D 5.10%、τ-eudesmol 11.38%、geranyl tiglate 5.16%。 2.Direct water distillation： linalool 16.89%、menthone 6.07%、β-citronellol 8.15%、geraniol 33.69%、aristolene 8.37%、germacrene D 0.42%、τ-eudesmol 7.34%、geranyl tiglate 5.51%。

碩士
國立中興大學
食品暨應用生物科技學系所
103
Essential oils are a complex mixture of plant secondary metabolites that may have anti-allergic, anti-inflammatory and anti-cancer effects. However, immunodualtory functions of steam distillation essential oils from plants remain unclear. Therefore, six potential plants including Glechoma hederacea, Calendula officinalis,Cymbopogon nardus, leaves of Cinnamomum osmophloeum Kanehira., Rosmarinus officinali and Coleus amboinicus Lour. were selected to extract their steam distillation essential oils for immunomodulatory study. First, effects of these essential oils on immunodualtory functions in vitro were evaluated by observing Th1/Th2 cytokines produced by primary splenocytes, pro- and anti-inflammatory cytokine secretions by peritoneal macrophages and the stability test to the degranulation of mast cells from BALB/c mice. The results showed that steam distillation essential oil of Coleus amboinicus among six essential oils had Th2-skewed but anti-immunodualtory responses to splenocytes, anti-immunodualtory effects on peritoneal macrophages and the better stability to the degranulation of mast cells. Thus,the essential oil was selected to perform animal study for its potential antiimmunodualtory and anti-allergic effects in vitro. Next, the potential essential oil with anti-immunodualtory and anti-allergic functions was further selected to administer to normal and ovalbumin (OVA)-sensitized and challenged BALB/c mice using inhalation intervention in vivo. In normal mice, the results showed that there were no significant differences among Th1/Th2 cytokine secretions and the profileration of splenocytes, no-specific antibodies in the serum and the degranulation of mast cells after inhalation intervention. However, IL-1β/IL-10 secretion ratios by peritoneal macrophages decreased, exhibiting anti- immunodualtory effects. Although high dose (6 mg/l) inhalation of Coleus amboinicus essential oil reduced protein contents in the trachea, the weight of the kidney also decreased. To avoid side effects, low (0.3 mg/l) and medium (1.2 mg/l) doses of Coleus amboinicus essential oil were further selected to treat OVA-sensitized and challenged mice. The results showed that inhalation intervention using Coleus amboinicus essential oil reduced eosinophilia infiltration and inflammatory mediators in the trachea, inhibited inflammatory reactions by macrophages, increased OVA-specific IgG2a/IgE antibody ratio secretions in the serum and stabilized mast cells degranulation in the lung. Overall,our results evidenced that inhalation intervention using Coleus amboinicus essential oil improved allergic asthma.

Essential oil, extracted from the leaves and twigs of Kunzea ambigua (Sm.) Druce, is increasingly in high demand by industry for its ‘soft, medicinal and soothing aroma’ and claimed muscle relaxant properties. Production is moving from wild-harvested to orchardised stands populated with germplasm selected from native flora based on higher yield and improved quality of oils. However, there is limited research regarding the growth and production of K. ambigua and kunzea essential oil. To produce large quantities of kunzea essential oil with a consistent, high quality profile for commercial size, agronomic and post-harvest management protocols need to be established. This study first investigated extraction technology and the potential to optimise the distillation time to maximise oil yield and produce kunzea essential oil with a targeted chemical profile. This study showed that the highest oil yield was collected between 30 and 60 mins, much of which was dominated by monoterpenes and oxygenated monoterpenes. Longer distillation times resulted in oil fractions that were relatively high in levels of sesquiterpenes and the bioactive component viridiflorol (22.45 %) which reached a maximum at 240 mins. Steam distillation requires large quantities of material to predict oil yield and quality which can be problematic when the amount of vegetation is limited, such as in the evaluation of young plants in a germplasm selection program. Experiments investigating the use of small-scale solvent extraction to extrapolate the quality of steam-distilled oil were also performed. Sample preparation (frozen or oven-dried at 40°C) and extraction solvents (petroleum ether and ethanol) were investigated. The ethanol extraction of frozen K. ambigua leaves was shown to effectively predict the oil yield and chemical constituents of steam distilled oil. This technique was used for selecting superior, high yielding cultivars which contained higher levels of viridiflorol (highly desired by the market). Kunzea is still predominantly wild-harvested in North East Tasmania, and the first step for establishing plantations is to choose superior clones. This study aimed to (i) compare the chemical constituents of ethanol extracts from wild-grown and cultivated kunzea and (ii) investigate the genetic variation in oil yield and chemical constituents of distilled oil, sourced from cultivated plants. Although the qualitative chemical composition of ethanol extracts from kunzea grown in the natural habitat was similar to that subsequently produced by their cloned progeny undergrown in ideal conditions, the results showed quantitative variability, and associated phenotypic factors. The amount of chemical components in kunzea extract was higher in cultivated plants compared to wild-harvested samples, possibly due to optimised growing conditions and plant age. The variations in oil yield and chemical profile among distilled oils from different germplasms grown under identical conditions, confirmed genetic variability within the wild populations, presenting the opportunity to selectively propagate and breed elite K. ambigua cultivars by appropriate plant selection. Intensity and season of harvest has significant impacts on the recovery of the plants and the quality and quantity of kunzea essential oil produced. The responses to the depth of cut at harvest (harvest intensity) of shallow (0.2m above ground) and deep-cut harvest (0.1m above ground), undertaken in early summer, were compared to uncut material (control). The cumulative above-ground biomass of shallow-cut was two-fold higher, relative to deep-cut treatment with a concomitant higher oil content in shallow-cut (1.84 ± 0.11% DW) compared to deep-cut treatment (1.54 ± 0.32% DW) in spring. In particular, deep-cut treatment resulted in the plants having inadequate resources for re-growth and essential oil biosynthesis. There was no seasonal variation in oil content while the kunzea essential oil extracted from autumn cropping showed enhanced levels of bioactive components such as 1-8 cineole and viridiflorol. Therefore, the recovery of biomass post-harvest is optimised by shallow-cut harvests and autumn cropping maximised oil quantity, yielding premium kunzea essential oil with enhanced levels of bioactive components. Essential oils are inherently volatile and contain thermolabile components. The retention of these chemicals is key to aroma quality. This study investigated the changes in oil colour and chemical compositions of kunzea essential oil over eight months of storage at -20°C (freezer), 4°C (refrigerator) and 20°C (room temperature), respectively. An additional influence with/without the light was also implemented at 20°C (room temperature). Colour indicated alterations in stored kunzea essential oil where poor storage conditions resulted in a loss of ‘greenness’ (a* values). This study also showed that lower levels of bicyclogermacrene and enhanced concentration of α-terpineol could be an indicator of degraded kunzea essential oil. Notably, kunzea essential oil exposed to light had significantly decreased components of germacrene D, β-caryophyllene, and α-humulene, probably due to thermal isomerisation. Overall, kunzea essential oil stored in a freezer or refrigerator (below 4°C) was the most stable and consistent in colour and chemical profile whereas there is evidence that some components may be oxidized when exposed to light with negative consequences for oil colour and quality. This thesis has provided for improved production strategies to maximise the quantity and quality of kunzea essential oil from the view of the extraction technique (distillation time), selection of superior cultivars, the productivity of crop (plant recovery and oil quantity/quality depending on harvest intensity and timing), and stability of oils. High market demand requires that more studies be undertaken, focused on increasing the oil quantity and quality through crop management with appropriate plant selection for a sustainable and profitable industry.

碩士
嘉南藥理大學
化粧品應用與管理系
106
Cymbopogon martinii belonging to the family Poaceae, belonging to the family Poaceae.Different extraction methods can affect the composition of essential oils, further affect the biological activity.Thus,this study extrated essential oils from Cymbopogon martinii leaf by steam distillation (SD) and solvent-free microwave extraction(SFME) and evaluated anti-bacterial,antioxidant,anti-inflammatory,and whitening characteristics of the oils.In addition,the effects of citronellal,citronellol,nerol and geraniol on the biological activity were compared. The results showed that the main constituents of SFME oil were citronellal (36.14%), geraniol (17.04%), citronellol (10.38%);the main components of SD oil were citronellal (22.36%), nerol (20.66%), citronellol (13.03%) by gas chromatography-mass spectrometry (GC-MS). In the antibacterial test, antibacterial effect of SD essential oil was better than SFME essential oil against S. aureus. In the anti-inflammatorry test, NO radical scavenging ability and 5-LOX inhibition test showed that SD essential oil was better than SFME essential oil. In the antioxidant test scavenging DPPH free radicals results showed that SFME essential oil was better than SD essential oil.While β-carotene-linoleic acid bleaching test showed that there was no significant difference between the two essential oil. In the whitening test, tyrosine inhibition test showed that SFME essential oil was better than SD essential oil.

A comparative study was undertaken of different extraction methods for the isolation of volatile organic compounds from Murraya koenigii (curry leaf plant). The techniques studied included the traditional methods of extraction, namely, Soxhlet and solvent extraction as well as steam distillation. The solvent–free extraction techniques of headspace analysis and headspace solid phase micro-extraction (HS-SPME) were also investigated. In the evaluation of SPME, two different fibre coatings, poly(dimethylsiloxane) and poly(acrylate), were compared. Preliminary work to determine the effect of extraction parameters, such as extraction time, was carried out. The volatile oils in the fresh leaves of Murraya koenigii were isolated by the above-mentioned extraction methods and analysed by gas chromatography-mass spectrometry. The main aroma contributing compounds were identified by comparison of their retention times with those of standards and their mass spectra with those of known compounds contained in the National Institute of Science and Technology Standard Reference Database 1A (NIST 98). The essential oil contained mainly terpenes: monoterpene and sesquiterpene hydrocarbons. The constituents were identified and only the five selected analytes of interest, a-pinene, β-pinene, a-phellandrene, β-caryophyllene and a-caryophyllene were quantified in three of the methods, namely solvent extraction, soxhlet extraction and steam distillation. From the quantitative determination of the compounds of interest, steam distillation favoured the extraction of β-caryophyllene. The solvent and Soxhlet extractions showed no significant differences between the quantities obtained for a- and β- caryophyllene. The steam distillation and Soxhlet methods showed similar quantities of a-caryophyllene extracted. The extraction of the monoterpenes, a-pinene, β-pinene, and a-phellandrene, was favoured by the Soxhlet method of extraction. Quantification was difficult with HS-SPME and headspace analysis. Headspace analysis proved effective in the detection of the very volatile analytes. Headspace-SPME combined with GC-MS was found to be suitable for the identification of both monoterpenes and sesquiterpenes of M. koenigii. From this study, solvent extraction and Soxhlet extraction were found to be superior to the other methods studied for the characterisation and quantitation of the volatile organic compounds in essential oils of Murraya koenigii.
Thesis (M.Sc.)-University of KwaZulu-Natal, Westville, 2010.

The electromagnetic absorption properties of plasmonic nanostructures were utilized to develop mesoscopic sites for highly efficient photothermal generation steam, SERS biosensing, and light-triggered cellular delivery uptake. Plasmonic nanostructures embedded in common thermal solutions produces vapor without the requirement of heating the fluid volume. When particles are dispersed in water at ambient temperature, energy is directed primarily to vaporization of water into steam, with a much smaller fraction resulting in heating of the fluid. Solar illuminated aqueous nanoparticle solution can drive water-ethanol distillation, yielding fractions significantly richer in ethanol content than simple thermal distillation and also produced saturated steam destroying Geobacillus stearothermophilus bacteria in a compact solar powered autoclave. Subwavelength biosensing sites were developed using the plasmonic properties of gold nanoshells to investigate the properties of aptamer (DNA) target complexes. Nanoshells are tunable core-shell nanoparticles whose resonant absorption and scattering properties are dependent on core/shell thickness ratio. Nanoshells were used to develop a label free detection method using SERS to monitor conformational change induced by aptamer target binding. The conformational changes to the aptamers induced by target binding were probed by monitoring the aptamer SERS spectra reproducibility. Furthermore, nanoshells can serve as a nonviral light-controlled delivery vector for the precise temporal and spatial control of molecular delivery in vitro. The drug delivery concept using plasmonic vectors was shown using a monolayer of ds-DNA attached to the nanoshell surface and the small molecular “parcel” intercalated inside ds-DNA loops. DAPI, a fluorescent dye, was used as the molecular parcel to visualize the release process in living cells. Upon laser illumination at the absorption resonance the nanoshell converts photon energy into heat producing a local temperature gradient that induces DNA dehybridization, releasing the intercalated molecules.

碩士
中原大學
化學工程研究所
105
Due to climate change and the increasing demand of water for industry, Taiwan frequently faces an acute problem of water scarcity in recent years. Therefore, much attention has been paid for using reclaimed water to solve the problem of water shortage. Based on the effluents of domestic sewage and industrial waste water are large and stable water resources, the production of reclaimed water from these effluents will have great potential. In this study, membrane distillation was used for effluent treatment from Dihua sewage treatment plant (STP) to produce the reclaimed water. Experiments were divided into direct contact membrane distillation (DCMD) pilot test and air gap membrane distillation (AGMD) laboratory module test, the former was used for long-term data obtained while the latter was designed to implement the cleaning test for fouled membrane. In addition, simulation analysis for energy consumption of AGMD to produce reclaimed water from STP was also carried out in this study. Pilot DCMD test using flat sheet module with ePTFE membrane was conducted under feed temperature at 60℃and Re= 9500 while the permeate side at 35℃and Re=3200.The flux decline obtained by 4 hours operation per day and 2 month continuous operation is not significant, its value being about 15 kg/m²hr. Based on the measurement of conductivity in feed and permeate, respectively, to determine the ion rejection, results showed that the ion rejection reaches 99%. By measuring the Cl- ion concentration, it appeared that the rejection was 99.9%. SEM-EDS analysis for fouled membranes showed that the fouling components are mainly from organic matters. Based on the COD, Cl- and NH4+ measured from the produced water, it clearly indicated that the water quality from MD is better than that by RO. Experimental results of AGMD showed that 0.1 wt% NaOH or 0.8 wt% EDTA-4Na solution can wash away the fouling on the membrane surface and the cleaned membrane has flux nearly same as that from virgin membrane. Based on Memstill® concept for heat recovery, the thermal energy consumption of AGMD was also estimated. Under the given conditions of flat plate module 1x1 m2 , temperatures of feed inlet and after heater were at 80 and 30℃, respectively, and the superficial flow velocity in the module channel was 0.01 m/s, the thermal energy consumption estimated was 106.8 kWh/m3 and the flux was 5.5 kg/m2hr.

Applications Study of Membrane Distillation for the Dairy Industry ii Abstract Membrane technology has been used for food processing for many years. Of the range of membrane technology types, membrane distillation is relatively new to industry. Membrane distillation (MD) is a thermal membrane separation process which was introduced in the 1960s. It is considered to be an alternative to conventional separation processes like distillation and membrane reverse osmosis (RO), and has been mostly studied for desalination and water treatment processes. Its application in the treatment of dairy process and waste streams has not, however, been fully explored. MD is regarded to offer potential to be a cost effective membrane technique for concentration of dairy process and waste streams and recovering useful water. Dairy waste treatment has become more important in dairy industry at present due to reasons such as importance of preserving water and reduction of waste produced. Therefore, it is important for the dairy industry to invest in cost effective and energy efficient membrane processes for dairy waste treatment to recover water and concentrate the waste streams. MD could be a useful membrane separation process which can concentrate the dairy waste streams and recover water. MD is a thermally driven separation process working on vapour pressure gradient across the hydrophobic porous membrane. The ability to harness thermal energy (either waste or heat flows within the dairy plant) is the key reason researchers are promoting MD as a cost saving compared to pressure driven processes like RO. In the basic operation of MD, the liquid to be treated is fed to one side of the membrane, but the hydrophobic nature of the membrane prevents the liquid from entering the membrane pores. The vapour transported from feed side to the permeate side is condensed and produces water. The aim of this study is to investigate specific applications of MD in the dairy industry and assess its viability to save water or offer benefits against competing technologies.