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Le dioxyde de chlore est l’agent de blanchiment le plus utilisé pour le blanchiment des pâtes chimiques lignocellulosiques. Son utilisation s’accompagne malheureusement de la formation d’ions chlorates, composés inefficaces pour le blanchiment, ainsi que d’importants rejets de DCO et d’organo-chlorés (AOX), nuisibles pour l’environnement. Cette étude a consisté à concevoir un nouveau stade de blanchiment au dioxyde de chlore (stade D) à pH non-conventionnel, économe en réactifs, et visant à réduire l’impact environnemental d’une séquence classique. Le travail a été effectué sur des pâtes kraft de résineux, obtenues après cuisson ou à différents stades de la séquence de blanchiment. Les résultats ont montré que l’efficacité du nouveau stade D était meilleure lorsqu’il était placé en fin de séquence. Après optimisation et incorporation de peroxyde d’hydrogène comme réactif complémentaire, les pâtes obtenues présentent des caractéristiques équivalentes à celles d’un blanchiment conventionnel, en termes de blancheur et de degré de polymérisation moyen viscosimétrique ; et ce, avec une réduction drastique de la pollution (70% des AOX et 20 % de DCO), et un gain économique substantiel en productivité de séquence (diminution de la température et du temps de réaction). L’étude chimique de la réaction du dioxyde de chlore effectuée par différentes techniques (spectroscopie RPE, RMN, FTIR, chromatographie HPAEC-PAD), a révélé la présence de radicaux hydroxyles en milieu alcalin, et mis en évidence les principales étapes du mécanisme à différents pH. / Chlorine dioxide is the most widely used bleaching agent for the production of bleached chemical pulps. However, its main drawbacks are the formation of chlorate ions which decrease delignification efficiency and the reject of toxic chloro-organic molecules (AOX) in mill effluents. This study focused on the development of a new bleaching stage using chlorine dioxide (D stage) at non-conventional pH, to reduce environmental impact and production costs. The work was carried out on several softwood kraft pulps after cooking, and at different stages of the bleaching sequence. The best results of the novel D stage were obtained for pulps at low kappa number, i.e. at the end of the bleaching sequence. The D stage was optimized and coupled with hydrogen peroxide addition. The same brightness and viscosimetric average degree of polymerization as after conventional D bleaching were obtained. Interestingly, a very important decrease of pollution load (70% of AOX and 20% of COD) was obtained, accompanied by a significant gain of productivity and energy saving (lower temperature and reaction time).Chemical investigations on the reaction mechanisms, carried out by different techniques (ESR, NMR and FTIR spectroscopies, HPAEC-PAD chromatography), revealed the formation of hydroxyl radicals at alkaline pH. The structural modification of the pulp residual lignin was also studied; differences of the reaction mechanism as function of pH were highlighted.

Made available in DSpace on 2014-06-11T19:24:46Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-07-08Bitstream added on 2014-06-13T19:11:27Z : No. of bitstreams: 1 martinelli_l_me_sjrp.pdf: 1675808 bytes, checksum: cfe68f960177993855a48c3037727299 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho foi construído e desenvolvido um secador de leito pulso-fluidizado que utilizou partículas inertes para a secagem de pastas e polpas de frutas. O sistema permitia o controle da vazão do ar de fluidização e de sua temperatura, da pulsação do ar e da vazão de injeção de pasta. Foram determinadas as curvas de fluidização de partículas de vidro e teflon no leito pulso-fluidizado sob diferentes configurações, bem como suas velocidades de mínima fluidização, as quais demonstraram-se próximas às curvas de um secador fluidizado convencional. Experimentos para a avaliação da agitação das partículas foram realizados para que fossem encontradas as melhores condições, determinando-se a existência ou não de pontos mortos no leito. Foi visto que as partículas pertenciam ao grupo D, segundo a classificação de Geldart (1973). Pasta de gesso foi seca no secador pulso-fluidizado para avaliação da produção de pó e do hold-up das esferas nas diferentes condições de operação, as quais tiveram como variáveis os períodos de injeção (fase ativa e inativa), ângulo da válvula borboleta que dava acesso do ar ao leito, temperatura do ar de secagem, velocidade do ar e vazão de pasta no leito. Foi observado que todas as variáveis testadas apresentaram influência na produção de pó e na quantidade de material aderido às partículas inertes. O secador pulsofluidizado foi testado também na secagem de suco e pastas de limão, maltodextrina e tomate, mostrando problemas de adesividade e, no caso de derivados de limão, aglomeração das partículas e colapso do leito. O secador foi utilizado ainda como vibro-fluidizado, quando o sistema de pulsação foi desligado e um sistema de vibração por eixos excêntricos foi acionado, constatando-se que o mesmo apresentou rendimento inferior ao pulso-fluidizado. Um secador do tipo spray dryer foi usado para a secagem... / For this work, a pulse fluidized bed drier that used inert particles for drying pastes and fruit pulps was constructed and developed. The system allowed for the control of fluidized air flow and its temperature, the air pulses and the paste injection flow. The fluidization curves and minimum velocity of fluidization of glass and Teflon particles were determined in the pulse fluidized bed. Experiments to evaluate the agitation of particles were done to find the best agitation conditions, determining the existence or not of dead spots in the bed. It was seen that the particles belonged to D group, as per Geldart (1973) classification. Plaster paste was dried in the pulse fluidized dryer to evaluate the production of powder and hold-up of the spheres under different operational conditions which were variations of the periods of paste injection (active and inactive phase), angle of the butterfly valve which gave air access to the bed, air drying temperature, air speed and paste flow. All tested variables influenced the powder production and the amount of material adhered to inert particles. The pulse fluidized bed drier was also tested for drying lemon juice and paste, maltodextrina and tomato, showing adhesive problems and, with the lemons, an agglomeration of particles and a collapsed bed. The dryer was also used as a vibro fluidized bed when the pulsation system was turned off and a vibration system with eccentric axles was set in motion, it was seen that the vibro fluidized bed had a lower yield than the pulse fluidized bed. A spray drier was used to dry lemon juice with maltodextrina, and it was found that a minimum of 65% of additional maltodextrina was needed. Physic-chemical testes were done from the powders obtained from the spray drying. These testes were for humidity, flowability, degree of agglomeration, higroscopicity, dispersibility, color determination and water activity... (Complete abstract click electronic access below)

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