Ce travail est consacré à l’étude du procédé de synthèse, d’extraction et de purification d’une hydrazine exocyclique à applications cosmétiques, la N-aminopyrrolidine (NAPY). Dans un premier temps, l’optimisation des conditions de synthèse par la voie Raschig e été conduite en étudiant l’influence de deux paramètres, rapport molaire des réactifs (NH2Cl, pyrrolidine) et la température, sur le rendement de la réaction. Les solutions brutes de synthèse étant très diluées (≈5%g en NAPY), l’extraction et la purification du produit utile sont souvent liées à des opérations successives de démixtion et de distillation. La détermination de ces conditions de séparation requière alors la connaissance des propriétés thermodynamiques des équilibres entre phases impliqués dans ces opérations unitaires. L’optimisation de la démixtion nécessite alors l’étude du système ternaire solide-liquide-liquide NaOH/Pyrrolidine/Eau. Trois coupes isothermes isobares ont été complètement déterminées, par ATI (Analyse Thermique Isopléthique) combinée à des dosages chimiques. La méthode du diamètre et des modules a été mise au point pour la détermination du point critique de la courbe de démixtion. Les opérations de distillation mettent en jeu le système ternaire NAPY/Pyrrolidine/Eau. Le binaire limite liquide-vapeur Eau/Pyrrolidine a été déterminé par ébulliométrie à la pression atmosphérique. Pour essayer de mieux comprendre les interactions hétéromoléculaires ayant lieu en phase liquide, deux autres binaire liquide-vapeur eau/amine ont été obtenus. L’étude su système ternaire liquide-vapeur nous a permis de déduire deux schémas de distillation possibles. Une fois les conditions de synthèse et d’extraction définies et un schéma de procédé a été proposé, la NAPY est obtenue conforme aux spécifications cosmétiques / This global work is related to the synthesis, extraction and purification of a new exocyclic hydrazine with cosmetic applications, the N-aminopyrrolidine (NAPY). Firstable, the optimization of the synthesis conditions by the Raschig way are carried out by studying the influence of two parameters, the reagents’ molar ratio and the temperature, on the yield of the reaction. Due to the very low hydrazine content in the reaction liquors (≈5%w of NAPY), the extraction and purification of the useful product are often linked to successive demixing and distillation operations. The determination of these separation conditions requires then the knowledge of thermodynamics’ properties of the phase equilibria in these unitary steps. The optimization of the demixing needs then the study of the solid-liquid-liquid ternary solution NaOH/Pyrrolidine/Water. In this aim, three isothermal isobaric sections were studied, by combination of ATI (Isoplethic Thermal Analysis) and chemical analysis. The diameter and modulus method was developed in order to determine the composition of the critical point of the demixing curve. The distillation steps involve the liquid-vapor ternary system NAPY/Pyrrolidine/Water. The limit binary system Water/Pyrrolidine was determined by ebulliometry under atmospheric pressure. For a better understanding of the heteromolecular interactions in the liquid phase, two others liquid-vapor binary systems Water/Amine were obtained. The study of the ternary liquid-vapor system lad us to deduce two various distillation schemes. Once the synthesis and extraction conditions defined, a global process scheme was proposed, and NAPY was obtained in conformity with the cosmetical specifications

Orientadores: Eduardo Augusto Caldas Batista, Antonio José de Almeida Meirelles / Dissertação (mestrado) - Universidade Estadual de Campinas, Fauldade de Engenharia de Alimentos / Made available in DSpace on 2018-08-17T21:09:08Z (GMT). No. of bitstreams: 1 Fonseca_LucianaAparecidaAndradePreviato_M.pdf: 1748931 bytes, checksum: 613a144c2469dfa664248bafa33dc2ac (MD5) Previous issue date: 2011 / Resumo: Dados de equilíbrio são úteis para o projeto e otimização de processos que envolvem separação de fases, como destilação e extração. Os álcoois superiores são subprodutos do processo de destilação relacionados com o aroma de bebidas alcoólicas e que, quando purificados podem agir como solvente. Esse estudo tem por objetivo a obtenção de dados isobáricos de Equilíbrio Líquido-Vapor (ELV) para sistemas binários e ternários envolvendo álcoois superiores. Dados de Equilíbrio Líquido-Vapor foram medidos para os sistemas binários compostos por 2-propanol/2-metil-1-butanol a 560 e 760 mmHg e para os sistemas ternários compostos por 2-propanol/1-butanol/3-metil-1-butanol e 2-propanol/2-metil-1-propanol/2-metil-1butanol, ambos a 760 mmHg. As medidas experimentais foram realizadas em ebuliômetro Fischer (VLE 602) e as composições das fases foram determinadas por cromatografia gasosa. A consistência termodinâmica dos dados de ELV binário P-T-x-y foi avaliada pelo teste de área e teste de van Ness-Fredenslund e os resultados comprovaram a boa qualidade dos dados de ELV determinados nesse trabalho. Os parâmetros de interação binária dos modelos NRTL, Wilson e UNIQUAC foram ajustados aos dados experimentais dos sistemas binários utilizando-se o software comercial Aspen Plus 12.1. Os resultados mostram uma boa descrição do ELV por esses modelos. Esses parâmetros foram ainda utilizados para descrever ELV dos sistemas ternários. Esses últimos resultados mostram uma boa concordância entre os dados experimentais e os calculados / Abstract: Equilibrium data are useful for design and optimization of processes involving phase separation, such as distillation and extraction. The higher alcohols are byproducts of the distillation process related to the flavor of alcoholic beverages and that when purified can act as a solvent. This study aims to obtain isobaric Vapor-Liquid Equilibrium (VLE) data for binary and ternary systems involving higher alcohols. Vapor Liquid Equilibrium were measured for the binary system composed by 2-propanol/2-methyl-1-butanol at 560 and 760 mmHg and for the ternary systems composed by 2-propanol/1-butanol/3-methyl-1-butanol and 2-propanol/2-methyl-1-propanol/2-methyl-1butanol, both at 760 mmHg. The experimental measurements were performed in a Fischer ebulliometer (VLE 602) and the phase compositions were determined by gas chromatography. Thermodynamic consistency of the VLE binary data P-T-x-y was evaluate by area test and van Ness-Fredenslund test and the results proved the good quality of the VLE data determined in this work. The binary interaction parameters of the NRTL, Wilson and UNIQUAC models were fitted to the experimental binary VLE data in the commercial software Aspen Plus 12.1. The results show a good description of the VLE data. These parameters were used to describe the VLE data for the ternary systems and the results show a good agreement between experimental and calculated data / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos