Institute of Paper Science and Technology / Thesis (Ph. D) -- Institute of Paper Science and Technology, 1998.

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Most metal ions have negative impacts on pulp mill operations. The concentrations of metal ions on pulp fibers and in washwaters rise significantly with increased wastewater recycling. The development of technology to remove these metal ions requires an understanding of how metal ions are bound to pulp components. It is also desirable to predict distribution of metal ions between the pulp fibers and the washwaters. The adsorption isotherms for eight metal ions (Ca, Ba, Mn, Zn, Pb, Cd, Ni, Na) were measured on bleached and unbleached (brownstock) kraft pulps at neutral pH and temperatures ranging from 25 to 75��C. On bleached pulps, the metal ion adsorption increased rapidly with increasing metal ion concentration in solution and then leveled off. At neutral pH, the adsorption on bleached pulp was stoichiometric to the carboxylate sites, whereas the adsorption on unbleached pulp was not, especially at high metal ion concentration in solution and low temperature. The pH isotherms specify the adsorption isotherms of sodium and calcium on wood pulps as pH ranging from 2.5 to 11.0. The pH isotherms on bleached pulp with only COOH functional groups (pK[subscript a] of 3.77) were saturated at pH 4 and above, whereas those on brownstock pulp with both COOH and PhOH (pK[subscript a] of 10) functional groups increased in two steps, at pH 4 and 8. The brownstock pulp is heterogeneous material. Therefore, only the empirical Freundlich model was applied to the data. To predict the metal ion adsorption on bleached pulps, two fundamental equilibrium models were developed: the multi-component ion exchange and the Donnan equilibrium models. The ion-exchange model better predicts the metal adsorption at neutral pH, whereas the Donnan equilibrium model more accurately predicts the pH isotherms. The adsorption kinetics of Ba����� and Ni����� were measured on wood pulps as a function of mixing speed, initial metal ion concentration, and temperature. The adsorption of metal ions reached equilibrium rapidly. The intraparticle diffusion model, based on first principle with a linear relationship assumption between adsorbed and free metal ion concentration, satisfactorily predicted the adsorption kinetics at low metal ion concentration in solution. / Graduation date: 2001

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Graduation date: 1997

Fume, sub-micron aerosal particles in the combustion gases, have been identified as a cause of extensive plugging and fouling in the heat transfer section of a kraft recovery boiler in kraft pulp mills. After the deposition on the heat transfer surface, fume deposits will undergo the sintering process which causes densification and hardening, making them hard to remove. There has been relatively little information available on the kinetics of the sintering of fume particles, and no information on the modeling of the sintering process of this particular material. No conclusion about the effect of chloride species on the sintering of fume particles has been made. A series of sintering tests in air at various temperatures were conducted using dense pellets made from a specific fume dust which contains a low amount of chlorides. Each pellet was heated at a constant temperature, ranging from 300��C to 550��C, for a different time interval. By the study of the microstructural change of each sintered specimen, the initial stage, intermediate stage, and final stage of sintering were identified. By the presence of an empirical constant K���, the relative linear shrinkage data in the initial stage sintering fit well with the model proposed by Kingery and Berg��� when volume diffusion is the controlling mechanism. By the presence of an empirical constant K2 and the application of grain growth data, the porosity-time data in the intermediate stage sintering fit well with the model proposed by Coble����� when volume diffusion is the controlling mechanism. The apparent activation energy obtained from the initial stage sintering is equal to 54.5 �� 27.7 kcal/mol which is in good agreement with the apparent activation energy obtained from the intermediate stage sintering which is equal to 56.0 �� 31.3 kcal/mol. A semi-empirical model for the sintering process of this particular well-packed fume dust was formulated. The model does not apply well to the loosely packed fume dust due to some unidentified factors The same experiment was carried out for the other fume dust which contains a high amount of chloride. By the use of the fractional density, the qualitative comparison of the sintering of the low chloride and high chloride dusts was made. At low temperatures, the sintering rate of the high chloride fume dust is lower than that of the low chloride fume dust. At high temperatures, both dusts have the same sintering rate and can sinter close to the theoretical density. It is postulated here that the retarded grain growth rate for the high chloride dust can improve the densification process in the intermediate stage sintering. / Graduation date: 1996

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An experiment was designed to test the hypothesis that each softwood pulp is unique and requires a specific, well defined mechanical treatment to derive its maximum strength potential. Three bleached softwood Kraft pulps and respective wood samples were sourced from both the Northern and Southern Hemispheres. The raw fibre characteristics of P. patula (Southern Hemisphere), P. menziesii (Northern Hemisphere) and P. mariana (Northern Hemisphere) were measured and compared. The raw pulp sheets were refined at different energies and intensities under controlled laboratory conditions using a 12” single disc pilot refiner. Results were assessed to determine the raw fibre characteristics, optimum refining conditions and the relative refined strength potential for each of the three samples. Results from anatomy measurements on the three wood samples differed significantly. P. patula exhibited a relatively high proportion of springwood growth in the early growing years. As the P. patula aged and formed mature wood there was a significant increase in the frequency of latewood formation. This was characterized by an abrupt and significant increase in the wall thickness, beyond that of the two Northern softwood samples. When the cell wall thickness increased, the lumen width and fibre diameter of the P. patula decreased significantly, yielding extremely coarse, stiff fibres. The Northern P .mariana and P. menziesii samples were characterized by a relatively consistent transition between high and low densities from the pith to the bark of the tree. The Southern P. patula had a unique density trend with an increasing frequency of high density peaks indicative of an increased latewood formation from the pith to the bark. The slower growing Northern P. menziesii and P. mariana samples did not have as clear a differentiation in fibre characteristics between juvenile and mature wood formation. The Northern samples did however contain a significantly higher proportion of juvenile latewood growth than the P. patula. However, the difference in fibre characteristics between earlywood and latewood formation was not as significant as that noted with the Southern P. patula Fibre morphology measurements on the unrefined bleached Kraft pulps also revealed significant differences between the three samples. The average MORFI LAB01 results on the P. patula defined fibres with a high coarseness and relatively low number of fibres per gram of pulp. The extremely coarse latewood fibres formed during mature wood growth being the most likely source. However, P. patula was also characterized with a high fibre flexibility and large lumen, characteristics consistent with earlywood fibres. The Pulmac Z-Span 3000 was used to define the individual fibre strength, when due consideration was given to the number of fibres per gram, the corrected Pulmac results suggested P. patula had the strongest fibres. When refined, using a standard disc refining programme, P. patula exhibited a fast freeness development. Conventional thinking would suggest that this was an indication of a weaker fibre. However, this species had a robust morphology compared to the Northern Hemisphere woods. The theory developed in this dissertation suggests that the effect of coarseness and the concomitant number of fibres per gram plays a significant role. These two parameters are not included in the “traditional” refining calculations. The applied refining load and intensity was calculated on the flow of the pulp passing through the refiner. The calculation did not consider the actual number of fibres present in that specific volume. The implication is that when a fixed refining load is applied to a pulp with coarse fibres there may be a higher effective load on those fewer fibres (resulting in fibre cutting and fines generation). In this case, the Northern samples have a comparatively low coarseness and more fibres per gram with each receiving a smaller portion of the total load and intensity. In terms of refined pulp properties, P. patula developed a relatively high bulk and tear index consistent with coarse, rigid fibres. The Northern P. mariana and P. menziesii samples produced a pulp with good tensile properties, consistent with a greater number of finer, collapsible fibres with a higher relative bonding area. P. patula fibres were extremely heterogeneous in nature containing the smallest relative lumen width during latewood formation and the largest lumen width during earlywood growth. As a result, P. patula contains extremes of both fine and coarse fibres in the same blend. It may be more beneficial for this species than the others to improve both the tear and tensile properties through fibre fractionation with appropriate development of the separate accepts and rejects streams. In terms of fibre development, low intensity refining parameters maximized the tensile strength of the Southern P. patula. The Northern P. mariana and P. menziesii samples had a greater number of fibres per gram of pulp requiring both a higher refining energy and intensity to develop the pulp to its maximum potential. To develop optimum tear results, high intensity refining, with a relatively low specific energy provided optimum results for all 3 samples. Results confirmed that there were significant differences in the fibre morphology both between the three different species and between the two Hemispheres. There was strong evidence that the fibre characteristics dictate the manner in which a fibre responds to refining which in turn determines the relative contribution to specific refined pulp properties. It may be possible to use fibre characteristics to determine the appropriate refining parameters for optimal fibre development which will enhance the value of the end product. To derive the maximum strength potential from P. patula pulp samples, it is recommended that further studies investigate Hydracyclone fractionation and the concomitant benefits of refining the separate streams. Furthermore, a separate study on fibre morphology and refining characteristics of the same species grown in both the Northern and Southern Hemisphere would provide valuable insight. / Thesis (M.Sc.Eng)-University of KwaZulu-Natal, Durban, 2009.

Graduation date: 1994