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- Effect of unbleached pulp kappa number on the kinetics of chlorine dioxide delignificationPublication . Simões, Rogério; Barroca, Maria J. M. C.; Castro, José Almiro A. M.Chlorine dioxide delignification of different unbleached kraft pulps from Eucalyptus globulus, having Kappa numbers of 12 to 18, was studied in the temperature range of 285 K to 358 K. The effect of the unbleached pulp Kappa number on the initial fast phase of delignification was investigated with respect to the depletion factors for Kappa number and chlorine dioxide concentration, as proposed by Barroca et al. Furthermore, the behaviour of the floor lignin content of the pulp, or the floor Kappa number, was analysed within this range. The results show that all pulps exhibit a similar pattern, with respect to temperature, in depletion factors for Kappa number and chlorine dioxide concentration. The degree of normalised delignification and chlorine dioxide consumption is very similar and independent of the Kappa number of the unbleached pulps. Moreover, the results reveal that there is a strong correlation between the floor lignin content and the temperature, and that this correlation is applicable to a wide range of unbleached pulp Kappa numbers, since the residual Kappa number is independent of its initial value. The results enable the general application of a kinetic model to kraft pulps with different unbleached Kappa numbers.
- Effect of carry-over on the kinetics of chlorine dioxide delignification of an unbleached hardwood kraft pulpPublication . Simões, Rogério; Barroca, Maria J. M. C.; Castro, José Almiro A. M.This work is concerned with the kinetics of the prebleaching stage of a kraft pulp of Eucalyptus globulus with chlorine dioxide. Its main purpose is to discuss the influence of the degree of washing, expressed as the COD of the pulp, on the kinetics and stoichiometry of chlorine dioxide delignification. The effect of the carry-over on the rate of delignification of a Do stage was studied over time for pulps with different initial organic charges (COD). A set of experiments was specially designed to discriminate the individual role of lignin and of COD upon the initial consumption of chlorine dioxide. A modified mathematical model, taking into account the reactions of chlorine dioxide with both lignin and the carry-over, has been developed. In this model, the initial chlorine dioxide consumption (in the fast phase of reaction) is dependent on two factors: the carry-over of the pulp and the temperature of operation. However, the carry-over does not affect the corresponding initial depletion factor for the Kappa number. The role of the dissolved organic material, carried with the pulp, upon the rate of reaction in the slow period is better described in the stoichiometry. The fit of the experimental results obtained for pulps with different COD reveals good prediction capabilities for both Kappa number and chlorine dioxide concentration in a conventional D0 stage.
- Ozone depolymerization of polysaccharides in different materialsPublication . Simões, Rogério; Castro, José Almiro A. M.The behaviour of polysaccharides contained in different cellulosic materiais is studied with respect to depolymerization by ozone in an aqueous medium. The ejJect of concentration in the liquid phase, temperature and time upon the depolymerization of holocellulose, bleached and unbleached pulps, microcrystalline and native celluloses is investigated. The viscosimetric degree of polymerization and lhe molecular weighl dislribulion are used to monitor the processo The resulls show that, allow values of temperature and pH, which inhibit the produclion ofradicals, the depolymerization rate is moderalefor lignin-free materiais. However, Ihis rale and its maximum exlent increase markedly with temperature. Moreover; the experiments suggest that the reactivity of ozone and the amounl of radicais in the system and its physical accessibility are the key factors to explain the observed depolymerization pro files. Finally, the results for lignin-free materiais are compared with those obtained with similar materiais but containing residuallignin, and this study confirms that lhe presence of lignin in the fibre matrix increases the depolymerization of the carbohydrates.