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Selection of high ethanol and sucrose tolerance zymomonas spp. /Sanae Kaewnopparat, Malyn Chulasiri, January 1984 (has links) (PDF)
Thesis (M.Sc. (Pharmacy))--Mahidol University, 1984.
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I. Indolin aus o-Amino-phenaethylamin.Schobel, Peter, January 1948 (has links)
Inaug.-Diss.--Basel. / Curriculum vitae.
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I. Indolin aus o-Amino-phenaethylamin.Schobel, Peter, January 1948 (has links)
Inaug.-Diss.--Basel. / Curriculum vitae.
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Reactive compatibilization of PBT/ABS blends by methyl methacrylate, glycidyl methacrylate, ethyl acrylate terpolymers /Hale, Wesley Raymond, January 1998 (has links)
Thesis (Ph. D.)--University of Texas at Austin, 1998. / Vita. Includes bibliographical references (leaves 255-263). Available also in a digital version from Dissertation Abstracts.
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Conversion of methyl ethyl ketone (MEK) to valuable chemicals over multifunctional supported catalystsAl-Auda, Zahraa Fadhil Zuhwar January 1900 (has links)
Doctor of Philosophy / Department of Chemical Engineering / Keith L. Hohn / The present work describes the conversion of bio-derived methyl ethyl ketone (MEK) into different useful chemicals.
The first part discusses the direct conversion of MEK to butene over supported copper catalysts (Cu-Al₂O₃, Cu-zeolite Y sodium (Cu-ZYNa) and Cu-zeolite Y hydrogen (Cu-ZYH)) in a fixed bed reactor. In this reaction, MEK is hydrogenated to 2-butanol over metal sites, and further dehydrated on acid sites to produce butene. Experimental results showed that the selectivity of butene was the highest over Cu-ZYNa, and it was improved by finding the optimum reaction temperature, hydrogen pressure and the percentage of copper loaded on ZYNa. The highest selectivity of butene (97.9%) was obtained at 270 °C and 20 wt% Cu-ZYNa. Over Cu-Al₂O₃, the selectivity of butenes was less than Cu-ZYNa since subsequent hydrogenation of butene occurred to produce butane. It was also observed that with increasing H₂/MEK molar ratio, butane selectivity increased. However, when this ratio was decreased, hydrogenation of butene was reduced, but dimerization to C₈ alkenes and alkane began to be favored. The main products over 20% Cu-Al₂O₃ were butene and butane, and the maximum selectivity of butene (87%) was achieved at an H₂/MEK molar ratio of five. The lowest selectivity of butene was obtained using Cu-ZYH, reaching ~40%. It was found that the amount of acidity in Cu-ZYH is much higher than in Cu-ZYNa (from (NH₃-TPD) measurements). This could have caused the selectivity of butene to decrease as a result of dimerization, oligomerization and cracking reactions.
The second part describes the conversion of MEK to higher ketones in one step using a multifunctional catalyst having both aldol condensation (aldolization and dehydration) and hydrogenation properties. 15% Cu supported zirconia (ZrO₂) was investigated in the catalytic gas phase reaction of MEK in a fixed bed reactor. The results showed that the main product was 5-methyl-3-heptanone in addition to 5-methyl-3-heptanol and 2-butanol with side products including other heavy products (C₁₂ and up). The effects of temperature and the molar ratio of reactants (H₂/MEK) on overall product selectivity were studied. It was found that with increasing temperature, the selectivity to C₈ ketone increased, while selectivity to 2-butanol decreased. The hydrogen pressure plays significant role on the selectivity of products. It was observed that with increasing the H₂/MEK molar ratio, 2-butanol selectivity increased due to hydrogenation reaction while decreasing this ratio leads to increasing aldol condensation products. In addition, it was noted that both conversion and selectivity to the main product increased using a low loading percentage of copper, 1% Cu-ZrO₂. The highest selectivity of 5-methyl-3-heptanone (~63%) was obtained at temperatures around 180 °C and a molar ratio of H₂/MEK of 2. Other metals (Ni, Pd and Pt) supported on ZrO₂ also produced 5-methyl 3-heptanone as the main product with slight differences in selectivity, suggesting that a hydrogenation catalyst is important for making the C₈ ketone, but the exact identity of the metal is less important.
The third part discusses the conversion of C₈ ketones to C₈ alkenes and C₈ alkane over a catalyst consisting of a transition metal (Cu or Pt) loaded on alumina (Al₂O₃). These bifunctional catalysts provide both hydrogenation and dehydration functionalities. The main products over 20% Cu-Al₂O₃ were a mixture of 5-methyl-3-heptene, 5-methyl-2-heptene and 3-methyl heptane. However, using 1% Pt-Al₂O₃ the major product was 3-methyl heptane with a selectivity reaching over 97% and a conversion of 99.9 %. Both temperature and the hydrogen pressure play an important role on the conversion of C₈ ketone as well as the selectivity of products (C₈ alkenes and C₈ alkane). Over 20% Cu-Al₂O₃, it was observed that increasing the reaction temperature led to an increase in the selectivity to C₈ alkane as a result of hydrogenation of the C₈ alkene. Also, it was observed that with an increase in H₂/C₈ ketone molar ratio, C₈ alkane selectivity increased. However, when this ratio was decreased, the further hydrogenation of C₈ alkene to C₈ alkane was reduced. The highest selectivity of C₈ alkene (81.7%) was obtained at 220 °C and a H₂/C₈ ketone molar ratio of 2. In addition, an experiment was carried out using a low loading percentage of copper, and it was noted that both conversion and selectivity to the main products decreased over 1% Cu-Al₂O₃. Over 1% Pt-Al₂O₃, C₈ alkane was the major product with different temperatures indicating that further hydrogenation of C₈ alkene was promoted on 1% Pt-Al₂O₃. At low temperature, for both Cu-Al₂O₃ and Pt-Al₂O₃, significant amounts of C₈ alcohols are formed because subsequent reactions do not proceed at a fast enough rate. Also using 1% Pt-Al₂O₃, the main product selectivity is still C₈ alkane with all H₂/C₈ ketone ratios.
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Modelagem e simulação do processo de produção do acrilato de etila / Modeling and simulation of the ethyl acrylate production processAmbrogi, Luiz Gustavo 08 October 2007 (has links)
Orientadores: Rubens Maciel Filho, Maria Regina Wolf Maciel / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T05:07:10Z (GMT). No. of bitstreams: 1
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Previous issue date: 2007 / Resumo: Para a síntese do acrilato de etila, foi desenvolvido um modelo contínuo bidimensional estacionário para um reator tubular, considerando transferência de calor e massa por dispersão radial e convecção axial. Foi assumido o modelo pseudo-homogêneo sendo do tipo ¿plug-flow¿, o qual se mostrou adequado para as condições de escoamento utilizadas. Todos os elementos necessários à modelagem detalhada do processo foram estabelecidos, incluindo informações experimentais, bem como as correlações para cálculo das propriedades físicas dos componentes puros, os métodos de cálculo respectivos à mistura, as correlações para estimativa dos parâmetros de transferência de massa e energia e a perda de carga. O modelo foi desenvolvido para trabalhar com diferentes métodos numéricos. Uma adimensionalização das variáveis foi realizada antes da discretização das equações diferenciais parciais pelo Método de Colocação Ortogonal. A solução numérica é baseada na implementação do Método das Linhas, o qual é uma combinação de um método de colocação ortogonal na dimensão radial e uma integração axial pelo método de Runge- Kutta de 4 ª ordem. Um método baseado na Quadratura de Gaus-Jacobi foi utilizado para o cálculo das médias das propriedades físicas na radial para cada intervalo de integração. O comportamento do reator é investigado em função de sua sensibilidade a um grupo de parâmetros de projeto e operação. Este software, que na verdade é uma planta virtual, foi utilizado para representar a produção do acrilato de etila em escala industrial em um reator multitubular. O catalisador utilizado foi ácido sulfúrico e as informações sobre a cinética foram suficientes para abordar várias operações compatíveis com as condições industriais. A reação é endotérmica, homogênea, possui uma cinética de segunda ordem e ocorre na fase líquida. A temperatura de reação utilizada foi em torno de 80 ºC, e o fluido de aquecimento utilizado foi o Dowterm A. Para etapa de separação utilizou-se um software comercial, no caso o Aspen Plus. Esta etapa compreendeu primeiramente a caracterização termodinâmica da mistura reacional, e em seguida, a simulação dos principais equipamentos utilizados na separação, visando a otimização do processo. O Acrilato de etila é um éster produzido a partir do ácido acrílico e do etanol. Ésteres acrílicos como este, são mundialmente utilizados para a produção de polímeros, os quais por sua vez, são utilizados principalmente na indústria de tintas e vernizes, adesivos, couro, papel, e tecidos. O que motivou este trabalho, foram os recentes avanços no desenvolvimento de uma rota bioquímica para a síntese do ácido acrílico, utilizando a cana de açúcar como matéria prima. Hoje o ácido acrílico é produzido pela oxidação do propeno, ou seja, uma rota petroquímica. Como o etanol também é produzido no Brasil a partir da cana de açúcar, com um preço muito competitivo comparado à via petroquímica, é possível desenvolver uma ¿rota verde¿, a qual pelos resultados encontrados, é interessante tanto do ponto de vista financeiro quanto ambiental / Abstract: For the synthesis of ethyl acrylate, a continuous bi-dimensional steady-state model for a tubular reactor is developed, considering heat and mass transfer by radial dispersion and axial convection. The model is pseudo-homogeneous and is assumed a plug flow type, which it quite reasonable for the used flow conditions. All the elements necessary to the detailed process modeling were established, including experimental information as well as the correlations to calculate the pure-component physical properties, the respective mixture properties calculations methods, the correlations to estimate heat and mass transfer parameters and pressure drop. The model is built and rearranged to be solved for different numerical methods. An adimensionalization of the variables was carried out before the discretization of the partial differential equations by Orthogonal Collocation method. The numerical solution is based on the method of lines implementation, which is a combination of an orthogonal collocation method in the radial dimension and an axial integration by an explicit 4th order Runge-Kutta method. A Gauss-Jacobi quadrature based method for the radial mean physical properties calculations is used as an internal procedure for each integration interval. This software, in fact a virtual plant, was used to represent the industrial scale production in a multitubular reactor. The catalyst used was sulfuric acid and the information about kinetic was available to cover a broad range of operations compatible with industrial conditions. The kinetic is of second order, homogeneous and the reaction is endothermic and it takes place in the liquid phase. The reactor temperature was about 80 ºC, and Dowtherm A was used as heater fluid. The commercial software Aspen Plus, was used for the separation step. This step includes firstly a thermodynamic characterization of reaction mixture, and after, the simulation of the major equipments used in the separation step, aiming the process optimization. Ethyl acrylate is an ester produced from acrylic acid and ethyl alcohol. Acrylic esters such this, are worldwide used, primarily for polymers production, mainly for coatings, paints, adhesives, and binders for leather, paper, and textiles. The motivation of this work, was the recent advances in the development of biochemical route for the synthesis of acrylic acid by the sugar cane. Today the acrylic acid is produced by the propene oxidation, or a petrochemical route. As the ethyl alcohol is already produced in Brazil by the sugar cane, in a very competitive price compared to petrochemical via, it is possible to develop a ¿green route¿, which by the results found, is both interesting in a financial and environmental point of view / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química
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Da formação e controle de carbamato de etila em aguardentes / Control and formation of ethyl carbamate in sugar cane spiritsCarlos Alexandre Galinaro 29 September 2011 (has links)
A legislação brasileira estabelece o limite de 150 µg/L para os teores de carbamato de etila (CE ou uretana) em aguardentes. O presente trabalho indica que os teores de carbamato de etila em aguardentes podem ser reduzidos em até 92% do teor original após as aguardentes serem submetidas a uma nova destilação. Para amostras de aguardente recém destiladas (coletadas in loco) foi possível constatar que o CE também se forma após a destilação, e que a formação completa-se após 10 dias. A luz difusa não influenciou, quer na constante de velocidade quer na concentração de CE final. Esta, entretanto demonstrou-se dependente da temperatura. Observou-se que a reação ocorre com kobs de (6,4 ± 0,5) x 10-6 /s, a 25°C e pH 4,5, sendo este valor independente da origem da aguardente e da radiação luminosa. Os parâmetros de ativação para esta reação foram ΔH‡ 34 kcal/mol, ΔS‡ - 69 cal/K e ΔG‡ 54 kcal/mol. Foi possível estimar que o teor de uretana formado no interior do destilador foi inferior a 60% do CE total. Estudos com aguardente nas quais foi adicionado KOCN, indicaram que ocorre a formação de uretana com kobs (8,60 ± 0,4) x 10-5 /s, a 25°C, pH 4,5, com ΔH‡ 20,6 kcal/mol, ΔS‡ - 96,1 cal/K e ΔG‡ 48,7 kcal/mol. Esta reação não foi influenciada pela radiação luminosa (250 a 500 nm), bem como pelo teor alcoólico da aguardente (0,29 a 15,7 mol/L). O rendimento no teor de CE aumentou em função do teor alcoólico do meio, atingindo um valor máximo a 60% v/v. Cálculos quânticos sugeriram que o HNCO é a molécula reativa. Os resultados experimentais colhidos até o momento sugerem a existência de uma reação paralela consumindo parte do HNCO e, portanto limitando kobs e a relação [CE]teórico / [CE]experimental. A adição de NaCN à aguardente também conduz a formação de uretana, mas com constante de velocidade inferior a observada para o KOCN. / Brazilian law establishes the limit of 150 µg/L for ethyl carbamate (EC, urethane) contents in sugar cane spirits. The present work indicates that the levels of ethyl carbamate in spirits may be reduced up to 92% of the original content after undergoing a new distillation. It was observed that EC is also formed after distillation in recent distillated samples collected in loco and that the EC formation is completed after 10 days. The light did not influence either the rate constant or the final EC concentration. However, the rate constant proved to be temperature dependent. It was observed that the reaction occurs with kobs (6.4 ± 0.5) x 10-6 /s at 25°C and pH 4.5, which value is independent of the spirits origin and light radiation. The activation parameters for this reaction were ΔH‡ 34 kcal/mol, ΔS‡ - 69 cal/K and ΔG‡ 54 kcal/mol. It was estimated that the concentration of urethane formed inside the distiller was less than 60% of total EC. Studies adding KOCN in sugar cane spirits indicated that the formation of urethane occurs with kobs (8.60 ± 0.4) x 10-5 /s at 25°C, pH 4.5, with ΔH‡ 20.6 kcal/mol, ΔS‡ - 96.1 cal/K and ΔG‡ 48.7 kcal/mol. This reaction was not influenced by light radiation (250 to 500 nm), as well as the alcohol content of spirits (0.29 to 15.7 mol/L). The yield on EC content increased according to the alcohol content of the medium; reaching a maximum value of 60% v/v. Quantum calculations have suggested that HNCO is the reactive molecule. The experimental results collected so far suggest the existence of a parallel reaction which consumes part of HNCO and therefore limits kobs and the relationship [CE]theorical / [EC]experimental. The addition of NaCN to sugar cane spirits also leads to urethane formation, although with lower rate constant compared to the one observed for KOCN.
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Synthèse, dégradation et bio-propriétés du polyglyoxylate d'éthyle / Synthesis, degradation and bio-properties of poly(ethyl glyoxylate)Belloncle, Benjamine 28 March 2008 (has links)
Ce travail porte sur l'étude du polyglyoxylate d'ethyle (PGEt) : sa synthèse, sa caractérisation et sa dégradation. Le PGEt a été obtenu par polymérisation anionique. Les conditions optimales font intervenir un amorçage par NE3 dans le CH2Cl2 à une température inférieure à -20°C. L'existence d'une température plafond (Tp = 310K pour [M]0 = 1M) nécessite l'utilisation d'agents de terminaison (phényl isocyanate ou bromure de 2-bromo-2-méthyl propionyle) afin d'obtenir des PGEt stables. La dégradation par hydrolyse in vitro du PGEt a été étudiée par RMN 1H, CES... Le mécanisme fait intervenir des coupures de chaines et des hydrolyses des esters. Les produits ultimes de dégradation identifiés sont l'éthanol et l'hydrate d'acide glyoxylique. Le caractère biodégradable du PGEt a été confirmé par respirométrie. Des études préliminaires de toxicité (sur des hématies, le nématode C. Elegans, et la croissance des plantes) n'ont pas révélé d'effet nocif du PGEt et de ses produits de dégradation. / This work focuses on the study of poly(ethyl glyoxylate) (PRtG), from its synthesis and its characterization to its degradation to some biological applications. The chosen conditions for PEtG's synthesis were initiated by an anionic way (NEt3) in presence of CH2Cl2. Because the ceiling temperature of the monomer (EtG) is low (7°C), it is necessary to block the hydroxyl ended groups generated in situ. The use of PhNCO leads to stables PEtG. The PEtG can be used as a macroinitiator of atom transfer radical polymerization (ATRP if it is wisely done. The copolymerization of styrene is then controlled. The degradation by in vitro hydrolysis of PEtG mainly led to ethanol and glyoxylic acid hydrate release. The biodegradable character of PGEt was assessed by a respirometric test and a preliminary study of toxicity (on red blood cells, worms and plants) revealed no significant effect at the concentrations generally used.
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A study of thermogelling PCL dispersion : towards an injectable colloidal cell delivery systemShahidan, Nur Nabilah January 2014 (has links)
This thesis present a study of thermo-gelling polycaprolactone (PCL) dispersion which consist of a mixture of PCL microspheres (MSs) and thermo-responsive, graft cationic copolymer. The PCL microspheres are solid or colloidosomes (hollow). This study aims toward an injectable colloidal cell delivery system. The thermo-responsive copolymer used in this study is a new family of cationic graft copolymer. The cationic graft copolymer consisted of cationic poly(N,N-dimethylaminoethyl methacrylate) backbone and poly 2-(2-methoxyethoxy) ethyl methacrylate (PMA) side chains. A series of new cationic graft copolymers were synthesized with different PMA arm length and grafting density. A representative copolymer showed good cell viabililty. The solid PCL MSs were prepared using solvent evaporation method. The MSs were mixed with the thermo-responsive graft copolymer. At room temperature the mixture were liquid-like and gelled at body temperature (37 ˚C). This indicates that the mixture systems were injectable. The injectable route offers a minimal invasive route to fill defect void inside the body. Furthermore, a porous morphology was evident for the mixed gels at 37 ˚C and the porosity could be altered using different composition of the mixed components. The mixed system showed self-healing properties for low volume fraction of PMA. The mixed system particle gel was more ductile in electrolyte but showed similar morphology to the mixed system particle gels prepared in water. This part of the study was carried out using PCL MSs prepared by cetyltrimethylammonium bromide (CTAB) as surfactant. A brief study using polyvinyl alcohol (PVA) as the surfactant showed that the PCL MSs had similar diameter and gel morphology which suggests that the model systems studied using CTAB may be applicable to the PVA system. Microencapsulation attracts interest due to its ability to deliver and control release actives and also its application in many fields. Colloidosomes are one of the microcapsules/microspheres used for microencapsulation. In this study a two step, facile and scaleable colloidosome preparation method was introduced. The PCL colloidosome shell consisted of partially fused small nanoparticles. The PCL colloidosomes were birefringence under cross polarised light due to the stress applied during solvent evaporation. A brief study showed that the mixture system of colloidosomes and thermo-responsive graft copolymer are able to gel at 37 ˚C.
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Structural and synthetic investigations of diterpenoid natural products from southern African marine invertebratesGray, Christopher Anthony January 2003 (has links)
This thesis is divided into two parts. The first part (Chapter Two) documents a bioassay guided investigation of the ethyl acetate extracts of four marine invertebrates from Mozambique (an Irciniid sponge, a Haliclona sp. sponge, an ascidian tentatively identified as Diplosoma sp., and the soft coral Cladiella kashmani). Eight known compounds [ilimaquinone (2.1), renierone (2.7), N-formyl-1,2-dihydrorenierone (2.8), 1,6-dimethyl-7-methoxy-5,8-dihydroisoquinoline-5,8-dione (2.9), mimosamycin (2.10) 7Z-allylidene-5-hydroxy-7,7a-dihydro-2H-cyclopenta[b]pyran-6-one (2.11), flaccidoxide (2.18) and 11S,12S-epoxycembra-1Z,3E,7E-trien-14S-ol (2.19)] and a new diterpene [13S,14R-diacetoxy-11S,12R-epoxycembra-1Z,3E,7E-triene (2.20)] were isolated and identified using standard spectroscopic techniques. Anomalies in the published spectral data of 2.1 and 2.8 were exposed and corrected, and the absolute stereochemistry of the cembrane diterpenes 2.18 and 2.20 established using the modified Mosher’s method. The comparative activities of the nine natural products against four cancer cell lines (A549, LOX, OVCAR3, SNB19) are reported. The second part of the thesis (Chapter Three – Chapter Six) is concerned with an ecological, structural and synthetic study of diterpenes from the endemic South African pulmonate limpet Trimusculus costatus. Two new labdane diterpenes [6b,7a-diacetoxylabda-8,13E-dien-15-ol (3.10) and 2a,6b,7a-triacetoxylabda-8,13E-dien-15-ol (3.11)] were isolated from T. costatus and evaluated for anti-feeding activity against the common predatory fish Pomadasys commersonnii. A strategy for the semi-synthesis of 3.10 from rhinocerotinoic acid (4.14), a diterpene reportedly present in the ubiquitous South African shrub Elytropappus rhinocerotis, was devised in order to allow further bioactivity tests to be performed and unequivocally assign the unknown absolute stereochemistry of the T. costatus metabolites. Attempts to isolate rhinocerotinoic acid from local specimens of Elytropappus rhinocerotis were unsuccessful, and as the repetition of a published synthesis of 4.14 from (-)-sclareol (4.15) gave rhinocerotinoic acid in unacceptably low yields with poor stereoselectivity, an improved synthesis of 4.14 is presented. Comprehensive studies using hispanone (5.1) as a model compound showed that 6,7-dioxygenated labda-8-enes could be prepared from compounds possessing a 7-oxo-labda-8-ene skeleton with some degree of stereocontrol. In the process, fourteen new hispanone analogues were prepared and most of these were tested for activity in a suite of ten agro-chemical assays. The novel compound 7b-hydroxy-9a-carbonitrile-15,16-epoxylabda-13(16),14-dien-6-one (5.34) exhibited significant activity against the crop fungus Phytophthora infestans and is currently being subjected to further agro-chemical tests. Unfortunately, the results from the oxygenation study performed on the model compound 5.1 could not be directly extrapolated to rhinocerotinoic acid. Attempts to prepare the naturally occurring 3.10 from 4.14 via an alternative route were unsuccessful but yielded an analogue of 3.10 in which the substituents at C-6 and C-7 are in a diequatorial rather than a diaxial configuration.
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