Organic solvent production plants emit waste gases containing volatile organic compounds (VOCs) which are usually harmful to the environments and public healths. Plant managers are obligated to control the VOC emission to meet regulations at reasonable costs. A solvent plant located in southern Taiwan emits VOC-containing gas streams from some distillation columns and storage vessels with a total ventilation gas flow rate of 2.6-3.6 m3/min which contains VOCs with concentrations of less than 1,000 mg C/m3. Due to a concern of plant¡¦s safety, the plant managers constructed a full-scale biofilter for eliminating a part of the VOCs and the associated odors in the waste gas. This study aimed to investigate the effects of operation parameters such as EBRT (empty bed retention time) of the gas through the biofiltration media and organic loading to the media on the VOC removal efficiency. The biofilter is constructed of RC (reinforced concrete) with outer dimensions of 8.45 mL ¡Ñ 3.30 mW ¡Ñ 3.00 mH. The filter was also instrumented with inverters for control of speed of induced fans, and with thermometers, hygrometers, and wind speed meters. Fern chips with a total packing volume of 36 m3 was used as the biofiltration media. After inoculation with suitable microorganisms, the waste gas was introduced to the filter for VOC elimination. Nutrients (urea, milk, and a phosphate salt) and water were supplemented to the media on a daily basis. The investigation period is July, 2008 to May, 2010. In the period, THC (total hydrocarbon) concentrations for the influent and effluent gases to and from the reactor were daily measured. In addition, on a weekly basis, compositions of the VOCs in gas samples were detected by a gas chromatography equipped with a flame ionization dector (FID). On the same time basis, pH, COD (chemical oxygen demand), SS (suspended solids) in a sample of the trickled liquid from the media was analyzed. Media pH and moisture content were also analyzed for understanding the environmental conditions around the microorganisms for the VOC degradation. Results indicated that the media was in conditions of pH = 4.5-7.0, moisture = 11-61 % in the experimental phase. Trickled liquid had low COD and SS contents which can be easily treated by the existing wastewater unit in the plant, or be recycled to the media. Avarage THC, NMHC (nonmethane hydrocarbon), and VOCs were 71, 73, and 79%, respectively, with gas EBRTs of 4.2-6.3 min. With media pH of 4-5 and moisture contents 51-57%, over 90% of the influent VOCs coulb be eliminated. However, nearly dried media (moisture around 10%) had VOC removal efficiencies of lower than 30%. Nutrition tests indicate that the VOC removal efficiency was nearly proportional to milk supplementation rate. Removal of ethnaol and acetic could easily be removed with an efficiency of over 97% while 2-pentane was only 74%. Odor intensities of the treated gas could be controlled to <1,000 (dilutions to threshold) according to 3 test data.

No description available.

Neste estudo foi investigada a alcoólise enzimática do óleo de soja com etanol, utilizando t-butanol como solvente e enzimas imobilizadas Lipozyme TL IM, Lipozyme RM IM e Novozym 435 como catalisadores. As reações foram realizadas em um reator batelada fechado acoplado a um condensador e com constante agitação. Foram avaliadas a influência do t-butanol, do tipo de enzima utilizada, da razão molar álcool/óleo e da temperatura no rendimento em biodiesel. A etanólise do óleo de soja por sucessivas adições de álcool foi investigada e as melhores condições foram obtidas em presença de t-butanol, razão molar etanol/óleo igual a 3, temperatura de 50C e 5% (m/m) de Novozym 435. Nas reações conduzidas em presença de t-butanol não foram observadas diferenças significativas entre a adição direta e a escalonada do álcool. Os efeitos da adição de álcool só foram observados na ausência de t-butanol. O rendimento máximo em ésteres etílicos atingido foi cerca de 66% após 4h de reação com Novozym 435 na presença de solvente. / In this research, the enzymatic alcoholysis of soybean oil was investigated by using commercial immobilized lipases: Lipozyme TL IM, Lipozyme RM IM and Novozym 435 as catalysts. The reactions were carried out in a closed batch reactor with constant stirring and coupled with condenser. The influence of t-butanol, type of enzyme, molar ratio (alcohol/soybean oil) and temperature on biodiesel yield were evaluated. The ethanolysis of soybean oil by stepwise additions of ethanol was also investigated. The best conditions were obtained in t-butanol presence with ethanol/oil molar ratio of 3, temperature of 50oC and 5 wt.% Novozym 435. For the reactions carried out with t-butanol, the effects of stepwise alcohol addition were not observed, but it was realized in t-butanol absence. The maximum biodiesel yield achieved was 66% after 4h of reaction with Novozym 435 in t-butanol system.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2014-12-29T15:35:19Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação - Tereza Cristina de Deus Honório - 2013.pdf: 1533455 bytes, checksum: 94b316a371dbbb095635e691df80c2b3 (MD5) / Approved for entry into archive by Erika Demachki (erikademachki@gmail.com) on 2014-12-29T15:40:31Z (GMT) No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação - Tereza Cristina de Deus Honório - 2013.pdf: 1533455 bytes, checksum: 94b316a371dbbb095635e691df80c2b3 (MD5) / Made available in DSpace on 2014-12-29T15:40:31Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação - Tereza Cristina de Deus Honório - 2013.pdf: 1533455 bytes, checksum: 94b316a371dbbb095635e691df80c2b3 (MD5) Previous issue date: 2013-03-19 / Introduction: Aromatic organic solvents (AOS) are widely used in diverse industrial and laborer activities among others involving manipulating of products likes lacquers, inks and varnishes. Among the most commonly used AOS are toluene, xylene, styrene, ethylbenzene and phenol. Occupational exposure to these compounds can cause damage to the body, which leads to a concern about the health of the worker. Biological monitoring is an important tool used to evaluate exposition to chemical substances in the work environment, that consists of quantify the biomarkers of occupational exposure in biological samples. Brazilian values of AOS biomarkers and maximum allowable biological index (IBMP) are described in the NR7 of the Brazilian legislation (Ministério do Trabalho e Emprego, MTE). Objective: The aim of this work was to validate technical in HPLC-PDA for quantifying the exposure’s biomarkers and than evaluate the exposure’s profile to toluene, xylene, styrene, ethylbenzene and phenol in workers exposed in university community. Methods: To analyze the AOS biomarkers in urine samples by HPLC-PDA, method validation was done according to the preconized parameters by ANVISA described in RE 899/2003. Participate of the study 30 occupationally exposed volunteers that provided urine samples and asked a questionnaire survey to characterize the sampling. The sampling’s characterization was done by applying a survey to volunteers. Both descriptive and multivariate statitical analysis was performed to the analytical and surveying data. Results: The analytical method was to validate and appropriated for the purposes established. About 3,3 % of the volunteers presented levels of hipuric acid above of the allowed by the law. Besides, it was detected 3,4-methylhipuric acids in 13,3 % of volunteers in concentration below the maximum allowable limit. The main symptoms reported were headache, dyspnea, numbness and cough. Conclusion: The analytical method was within acceptable limits. It was observed that higher levels of hippuric acid in volunteers may be linked to a lack of protective equipment and collective environmental protection equipment, and high weekly workload. Additionally, methyl hippuric acid was found below IBMP. It was demonstrated a correlation between exposure to AOS biomarkers and symptoms reported by the volunteers. / Introdução: Os solventes orgânicos aromáticos (SOA) são substâncias amplamente utilizadas em várias atividades industriais laborais, dentre outras que envolvem a manipulação de produtods como tintas, vernizes e lacas. A exposição ocupacional a estes compostos pode causar danos à saúde, o que leva a uma preocupação em relação à saúde do trabalhador. Dentre os solventes aromáticos utilizados, citam-se, pela elevada frequência de exposição, o tolueno, o xileno, o estireno, o fenol e o etil-benzeno. Uma das ferramentas utilizadas para avaliar a exposição ocupacional a agentes químicos é a monitoração biológica que se baseia na quantificação de biomarcadores de exposição ocupacional. Os marcadores disponíveis e os valores de índice biológico máximo permitido (IBMP) se encontram descritos na NR 7 do Ministério do Trabalho e Emprego do Brasil (MTE). Objetivo: O objetivo do trabalho foi validar técnica analítica em HPLC-PDA para quantificar os biomarcadores de exposição aos SOA para avaliar o perfil de exposição ao tolueno, xileno, estireno, etilbenzeno e fenol em voluntários expostos em comunidade universitária. Métodos: Para a quantificação dos biomarcadores dos SOA, realizou-se a validação analítica do método por HPLC-PDA seguindo parâmetros estabelecidos pela RE 899 da ANVISA. Participaram do estudo 30 voluntários expostos aos SOA, os quais fornecerem amostra de urina, além de responderem a um questionário antropométrico e sócio-epidemiológico ocupacional para a caracterização da amostragem. Utilizou-se análise estatística descritiva para a validação analítica e análise multivariada para os dados obtidos do questionário. Resultados: O método analítico foi validado e adequado para os propósitos definidos. Os resultados demonstraram que 3,3 % dos voluntários apresentaram níveis de ácido hipúrico acima dos limites estabelecidos pela legislação e 13,3 % apresentaram níveis de ácido hipúrico acima dos valores de referência e abaixo do Indice Biológico Máximo Permido. Os ácidos 3 e 4- metilhipúricos foram detectados em 16,6 % dos voluntários e as concentrações desses metabólitos estavam abaixo dos limites de tolerância estabelecidos pelo MTE. Os principais sintomas reportados foram cefaleia, dispneia, parestesia e tosse. Conclusão: O método analítico estava dentro dos limites aceitáveis. Observou-se que a elevação dos níveis de ácido hipúrico nos voluntários pode estar ligada à falta de equipamentos de proteção coletiva no ambiente e de equipamentos de proteção individual, além de elevada carga horária de trabalho. Adicionalmente, o ácido metilhipúrico encontrado estava abaixo do IBMP. Demonstrou-se correlação entre exposição a SOA, biomarcadores e sintomatologia relatada pelos voluntários.

This thesis explores the robustness and the versatility of pressurized hot water extraction (PHWE) for a variety of analytes and matrices. Applications discussed include: selective extraction of alkaloids in goldenseal followed by their degradation studies; in-cell clean-up of pesticides in medicinal plants employing custom made molecularly imprinted polymers (MIPs) sorbents; in-cell pre-concentration followed by desorption of aflatoxins in plants with MIPs; desorption of pesticides from electrospun nanofiber sorbents; and removal of templates from MIPs sorbents. It was demonstrated that selective extractions could be achieved by just changing the temperature of water while adjusting the pressure. For instance, the alkaloids in goldenseal (hydrastine and berberine), were extracted at 140 °C, 50 bars, 1 mL min⁻¹ in 15 min; organochlorine pesticides from medicinal plants were extracted at 260 °C, 80 bars, 1 mL min-1 in 10 min; while aflatoxins AFG2, AFG1, AFB2 and AFB1 were extracted at 180 °C, 60 bars and a flow rate of 0.5 mL min⁻¹ in 10 min. The selectivity of PHWE was further enhanced by combining it with selective MIPs sorbents at higher temperatutes. In-cell clean-up of interfering chlorophyll was successfully removed from the medicinal plants during pesticides analysis while clean-up of aflatoxins AFG2, AFG1, AFB2 and AFB1 was achieved in two extraction cells connected in series. Ultrasound was also combined with PHWE for extraction of hydrastine and berberine at 80 °C and 40 bars in 30 min. PHWE was further evaluated for removal of templates from quercetin, phthalocynine and chlorophyll MIPs. The templates were thoroughly washed off their MIPs within 70 min with PHWE compared to over 8 h for Soxhlet and ultrasound assisted extraction. Pesticides were also desorbed from electrospun nanofibers at 260 °C, 80 bars in 10 min employing only water at 0.5 mL min⁻¹. In the light of green chemistry, the decrease in the usage of organic solvents was 100%, resulting in no organic solvent waste.

Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.

Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.

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The first goal of this work focused on the development of an amine dehydrogenase (AmDH) from a leucine dehydrogenase using site-directed mutagenesis. We aimed at reductively aminating a prochiral ketone to a chiral amine by using leucine dehydrogenase (LeuDH) as a starting template. This initial work was divided into two stages. The first focused mutagenesis to a specific residue (K68) that we know is key to developing the target functionality. Subsequently, mutagenesis focused on residues known to be in close proximity to a key region of the substrate (M65 and K68). This approach allowed for reduced library size while at the same time increased chances of generating alternate substrate specificity. An NAD+-dependent high throughput assay was optimized and will be discussed. The best variants showed specific activity in mU/mg range towards deaminating the target substrate. The second goal of this work was the development of a thermostable glucose dehydrogenase (GDH) starting with the wild-type gene from Bacillus subtilis. GDH is able to carry out the regeneration of both NADH and NADPH cofactors using glucose as a substrate. We applied the structure-guided consensus method to identify 24 mutations that were introduced using overlap extension. 11 of the tested variants had increased thermal stability, and when combined a GDH variant with a half-life ~3.5 days at 65℃ was generated--a ~10⁶increase in stability when compared to the wild-type. The final goal of this work was the characterization of GDH in homogeneous organic-aqueous solvent systems and salt solutions. Engineered GDH variants showed increased stability in all salts and organic solvents tested. Thermal stability had a positive correlation with organic solvent and salt stability. This allowed the demonstration that consensus-based methods can be used towards engineering enzyme stability in uncommon media. This is of significant value since protein deactivation in salts and organic solvents is not well understood, making a priori design of protein stability in these environments difficult.