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Two liquid-solid reactions, in which the morphology of the solid changes as the reactions proceeds, were examined. One is the NA conversion in oil by decarboxylation on metal oxides and carbonates, and the other is the Kraft pulping in which lignin removal by delignification reaction. In the study of the NA conversion, CaO was chosen as the catalyst for the kinetic study from the tested catalysts based on NA conversion. Two reaction mixtures, carrier oil plus commercial naphthenic acids and heavy vacuum gas oil (HVGO) from Athabasca bitumen, were applied in the kinetic study. The influence of TAN, temperature, and catalyst loading on the NA conversion and decarboxylation were studied systematically. The results showed that the removal rate of TAN and the decarboxylation of NA were both independent of the concentration of NA over the range studied, and significantly dependent on reaction temperature. The data from analyzing the spent catalyst demonstrated that calcium naphthenate was an intermediate of the decarboxylation reaction of NA, and the decomposition of calcium naphthenate was a rate-determining step. In the study on the delignification of the Kraft pulping, a new mechanism was proposed for the heterogeneous delignification reaction during the Kraft pulping process. In particular, the chemical reaction mechanism took into account the heterogeneous nature of Kraft pulping. Lignin reacted in parallel with sodium hydroxide and sodium sulfide. The mechanism consists of three key kinetic steps: (1) adsorption of hydroxide and hydrosulfide ions on lignin; (2) surface reaction on the solid surface to produce degraded lignin products; and (3) desorption of degradation products from the solid surface. The most important step for the delignification process is the surface reaction, rather than the reactions occurring in the liquid phase. A kinetic model has, thus, been developed based on the proposed mechanism. The derived kinetic model showed that the mechanism could be employed to predict the pulping behavior under a variety of conditions with good accuracy. / Chemical Engineering

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In a kraft recovery dissolving tank, high temperature molten smelt droplets fall into an aqueous solution and dissolve. The rapid heat transfer between molten smelt and water can lead to violent dissolving tank operation, and in severe cases, a dissolving tank explosion. In this study, an experimental apparatus was built to investigate the interaction between a molten synthetic smelt droplet and water. Smelt-water interaction was documented, and the effects of water and smelt temperatures on droplet explosion probability, explosion delay time, and explosion intensity were examined. The results show that explosions always occur below a lower critical water temperature, which is a function of smelt temperature, and never explodes above an upper critical water temperature. Up to the upper critical water temperature, as the water temperature increases, the explosion probability decreases, and the explosion delay time and the explosion intensity increases. A Smelt-Water Interaction Temperature (SWIT) diagram was constructed to describe the explosion probability at different smelt and water temperatures.

In a kraft recovery dissolving tank, high temperature molten smelt droplets fall into an aqueous solution and dissolve. The rapid heat transfer between molten smelt and water can lead to violent dissolving tank operation, and in severe cases, a dissolving tank explosion. In this study, an experimental apparatus was built to investigate the interaction between a molten synthetic smelt droplet and water. Smelt-water interaction was documented, and the effects of water and smelt temperatures on droplet explosion probability, explosion delay time, and explosion intensity were examined. The results show that explosions always occur below a lower critical water temperature, which is a function of smelt temperature, and never explodes above an upper critical water temperature. Up to the upper critical water temperature, as the water temperature increases, the explosion probability decreases, and the explosion delay time and the explosion intensity increases. A Smelt-Water Interaction Temperature (SWIT) diagram was constructed to describe the explosion probability at different smelt and water temperatures.

A indústria de papel e celulose convive com questões de adequação da oferta à demanda que influenciam na tomada de decisão em vários elos da cadeia produtiva. A pressão por baixos custos requer novos investimentos em tecnologia, normalmente associados ao processo e ao produto. Neste cenário, o objetivo do presente trabalho envolve o estudo da influência de variáveis de processo sobre a composição química da polpa e do licor preto, bem como sobre a formação de ácidos hexenurônicos, na polpação Kraft industrial de Eucalyptus. A metodologia proposta contemplou a realização de 36 polpações (em duplicata), sendo 3 níveis de álcali ativo (14, 17 e 19%), 2 níveis de sulfidez (20 e 30%) e 3 níveis de temperatura (150, 160 e 170oC). As polpas obtidas foram analisadas quanto à composição química, alvura e viscosidade. Os licores gerados no processo foram analisados quanto à composição química e por espectroscopia no infravermelho. Os resultados obtidos indicaram que uma maior sulfidez gera um menor teor de ácidos hexenurônicos na polpa independentemente da carga de álcali empregada. A temperatura exerce forte influência na geração destes ácidos, sendo que a 160°C foram geradas as maiores concentrações de ácidos hexenurônicos na polpa. Ainda com relação à temperatura, observou-se que o número kappa da polpa é reduzido quando a temperatura é elevada. A carga de álcali ativo leva a um aumento na quantidade de ácidos hexenurônicos gerados na polpa e a uma redução do número kappa. A alvura da polpa foi mais elevada para menores teores de ácidos hexenurônicos. A utilização da técnica de espectroscopia no infravermelho não se mostrou aplicável para a determinação dos teores de lignina nos licores de cozimento. / The pulp and paper industries have to manage issues concerning the offer of their products and the needs of different markets. To get this goal several important aspects of the productive chain has to be considered. The achievement of low costs of production requires investments in technologies for both processes and products. In this context, the aim of the present work involves the study of the influence that process parameters exerts in the chemical composition of the pulps and liquors, as well as hexenuronic acids generated in the industrial kraft pulping of Eucalyptus. The experimental work consisted in a factorial planning designed pulping reactions. 36 cookings were performed (in duplicate) with 3 levels of active alkali (14, 17 e 19%), 2 levels of sulfidity (20 e 30%) and 3 levels of temperature (150, 160 e 170oC). The obtained pulps were analyzed in relation to their chemical composition, brightness and viscosity. The black liquors were also analyzed by infrared spectroscopy. The results indicated that the higher sulfidity produced pulps with the lower content of hexenuronic acids, independently of the charge of active alkali employed in the process. The temperature of the pulping process exerted a strong influence in the production of hexenuronic acids, mainly at 160°C. Still considering the temperature, it was observed that occurs a reduction of the kappa number at higher temperatures. The active alkali charge produced an increase in the amount of hexenuronic acids and a decrease in the kappa number of the pulps. It was also observed an increase in the brightness for the pulps with lower amount of hexenuronic acids. Infrared spectroscopy showed not feasible results considering the determination of lignin content in the pulping liquors.

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