Akademisk avhandling--Teknisk kemi--Åbo, 1980. / Résumé en anglais, allemand et russe. Notes bibliogr.

No description available.

Thesis (B.S.)--Virginia Polytechnic Institute, 1944. / Includes bibliographical references (leaves 40-43). Also available via the Internet.

Estágio realizado na Portucel Viana e orientado pelo Eng.º Mário Amaral / Tese de mestrado integrado. Engenharia Química. Faculdade de Engenharia. Universidade do Porto. 2009

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The investigation was undertaken to effect a separation of the resin acids from the fatty acids of tallol a waste product of the paper industry. The furfural-water and furfural-petroleum ether methods were investigated. In the first method, a 5% solution of water in furfural by weight was used as a polar solvent with solvent to tallol ratios of 1-1, 2-1, and 3-1 by weight and attempting to induce crystallization by allowing the solution to stand at a temperature of about 26°C., chilling the solution to 2°C. for about 72 hours, and distilling about 50% of the solvent from the solution. No crystallization was evident in any of the solutions. In the second method, solutions of tallol and petroleum ether were agitated with furfural. The petroleum ether to tallol ratio was 10-1 by weight, and the furfural to tallol ratios were 1/2-1, 1-1, 1-1/2 - 1, 2-1, and 3-1 by weight. After agitation the solutions were allowed to stand at approximately 26°C., and then the two layers formed were separated by decantation. The petroleum ether layers were distilled, and the residues allowed to stand at about 26°C. Crystals appeared in three days and were recovered by centrifuging the residues. These crystals with yields carrying between 1.0% and 6.0% were identified by their melting point of 155-159°C., molecular weight determination as approximately 306, reactions with various reagents, and pertinent crystallographic data. / M.S.

Orientador: Ulf F. Schuchardt / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-09T20:28:05Z (GMT). No. of bitstreams: 1 Sales_HenriqueJorgeSousa_D.pdf: 2216336 bytes, checksum: 8961d924bfe31e720b51411a6194bd10 (MD5) Previous issue date: 2007 / Resumo: Neste trabalho, estudamos a esterificação seletiva química e enzimática para a separação dos esteróis, ácidos resínicos e ácidos graxos do resíduo oleoso de madeira, o Crude Tall Oil (CTO). A reação de esterificação enzimática (Candida antartica, lípase do tipo B) foi otimizada utilizando-se um planejamento fatorial 2. Os fatores estudados foram o tempo de reação (h), a temperatura da reação (°C), o teor de catalisador (%), o teor de metanol (%) e o teor de água (%). Com o aumento da temperatura de 24 para 60 °C observamos uma redução média na taxa de conversão de 26,6 %. O aumento da percentagem de metanol de 5 para 15 % também apresentou um efeito negativo na taxa de conversão de 13,1 %; isso indica uma inativação térmica (com a aumento da temperatura) e uma inativação do sítio ativo da enzima pelo metanol. O aumento da porcentagem de água de 0 para 15 % e do tempo de reação de 6 para 24 h apresentou um aumento de 31,2 e de 8,1 %, respectivamente, para a conversão. A interação entre a água e o metanol apresentou um efeito positivo de 22,5 % sobre a conversão, sendo que a melhor condição foi a de efetuar a reação à baixa temperatura (24 °C) com altos teores de água (10-15%) e metanol (10-15%). A adição do metanol em duas etapas também favoreceu a reação, devido ao efeito de desativação que o metanol tem sobre a enzima. O processo foi implementado em produção, onde 13,7 tons de CTO foram esterificadas em um tanque de 25 m e, após 166 h de reação, o índice de acidez caiu de 153,5 para 57,4 mgKOH/g. Através das análises do teor de ácidos resínicos livres, constatamos a total esterificação dos ácidos graxos presentes no CTO. O catalisador enzimático foi adsorvido em polipropileno e foram produzidos dois catalisadores heterogêneos com 0,2 g/g e 0,5 g/g; a relação 0,2 g/g foi a que apresentou a melhor relação custo-benefício para as reações em batelada. O catalisador heterogêneo foi empacotado em uma coluna, e essa foi utilizada para os experimentos de esterificação contínua. O catalisador se mostrou estável por mais de 50 dias. Comparando a performance do processo enzimático x processo químico, o catalisador enzimático apresentou melhor produtividade e seletividade. O resíduo obtido pelo fracionamento em um evaporador thin film apresentou um alto teor de esteróis livres (1,83%) e esteróis esterificados (22,31%). A fração leve do CTO esterificado foi fracionada em uma coluna de destilação piloto. Com este novo processo, obtivemos ésteres metílicos com alto grau de pureza e isento de contaminação por ácidos resínicos. No processo de purificação por destilação, obtivemos ácidos resínicos com 72,3% de pureza. O processo de esterificação seletiva e de fracionamento do CTO foi patenteado pela Cognis do Brasil. / Abstract: A process for obtaining fatty acid alkyl esters, rosin acids an sterols from Crude Tall Oil was developed. As first process step, a chemical or enzymatic esterification has been proposed. It has been shown that the enzymatic esterification of crude tall oil is technically and economically feasible. A 2 experimental design, to optimize the enzymatic process, was done. The factors studied were; reaction time (h), temperature (°C), catalyst (%), methanol (%) and water (%). Increasing the temperature to 60 °C, the conversion decreased 26.6%. The use of high amount of methanol resulted on a conversion of 13.1%. The increase of reaction time and amount of water improved the conversion in 8.1 % and 31.2 %. The best conditions found were reaction time (24 h), temperature (25 °C), water (10-15 %) and methanol (10-15 %). Dosage of methanol must be used because with higher amount of alcohol occurs deactivation of the enzyme. The laboratorial scale experiments were successfully, transferred to a 25 m pumped reactor in the industrial plant. An acid value reduction from 153.5 to 57.4 in 166 hrs could be achieved. Using an immobilized biocatalyst, 0.2 g/g and 0.5 g/g, experiments in a stirred reactor have been performed. The best results were obtained with the 0.2 g/g catalyst system. The biocatalyst was used for successive batches. A continuous process in a column was successfully performed in laboratorial scale. The column was stable for more then 50 days in continuous operation. We compared the performance of enzymatic and chemical esterification. The enzymatic process has better productivity than the chemical process. The separation of the methyl esters and rosin acids from the sterol borates by thin film distillation produced a pitch with (1.83 %) of free sterols and (22.31 %) of total sterols. The separation of the methyl esters from the rosinic acids by distillation produced a high purity methyl ester free of resinic acids and a resinic acid with 72.3 % of purity. The process consists of five steps: 1- Enzymatic and chemical esterification of the tall oil fatty acids with methanol to convert the TOFA in methyl esters; 2- Stripping of water/methanol; 3- Esterification of the free sterols with boric acid. 4- Separation of the methyl esters and rosinic acids from the sterol borates by distillation and 5- Separation of the methyl esters from the rosinic acids by distillation. The process was patented by Cognis Brasil. / Doutorado / Quimica Organica / Doutor em Ciências

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Thesis (Ph. D.)--Institute of Paper Chemistry, 1943. / Bibliography: leaves 69-72.

Abstract Moisture content control is a very effective way of protecting timber. Treatments with environment-friendly, biodegradable tall oil are known to reduce the capillary water uptake of pine sapwood greatly, but despite the good results achieved there have been two problems that limit the use of tall oil for wood protection, the large amount of oil needed and the tendency for the oil to exude from the wood. This work was undertaken in order to obtain an understanding of the mechanism of wood protection by means of crude tall oil (CTO) and to find technical solutions to the main problems limiting its use for industrial wood protection. It is shown that the emulsion technique is one way of solving the first problem, as it provides high water-repellent efficiency at considerably lower oil retention levels. The fact that water is used as a thinner in this technique instead of the commonly used organic solvents is beneficial from environmental, economic and safety points of view. It is also shown that although the drying properties of CTO are inadequate for use as such in wood preservation, its oxidation and polymerization can be accelerated considerably by means of iron catalysts, which prevent the oil from exuding out of the wood. This also increases the water repellent efficiency of CTO treatment. Most impregnation oils do not dry when applied in large quantities, because they hinder the diffusion of air through the wood, which supplies the necessary oxygen. Limiting of the oil uptake by the means of the emulsion technique disturbs the airflow to a lesser extent, and thus enhances the drying process. Hence, both the emulsion technique and the use of an iron catalyst improve both the water-repellent efficiency of tall oil treatment and the rate of drying of the oil, thus solving the two main problems related to wood impregnation with tall oil in one single-stage treatment which can be used in existing wood preservation plants. This is advantageous from both an industrial and an economic point of view.