Abstract The objective of this thesis was to obtain new information about mechanisms of thermomechanical pulp refining in the inner area of a refiner disc gap by studying inter-fibre refining and by calculating the distribution of energy consumption in the refiner disc gap. The energy consumption of thermomechanical pulping process is very high although theoretically a small amount of energy is needed to create new fibre surfaces. Mechanisms of refining have been widely studied in order to understand the high energy consumption of the process, however, phenomena in the inner area of disc gap has had less attention. It is likely that this important position is causing high energy consumption due to the high residence time of pulp located there. The power distribution as a function of the refiner disc gap was calculated in this work. The calculation was based on mass and energy balances, as well as temperature and consistency profiles determined by mill trials. The power distribution was found to be dependent on segment geometry and the refining stage. However, in the first stage refiner with standard refiner segments, a notable amount of power was consumed in the inner area of the disc gap. Fibre-to-fibre refining is likely to be the most important mechanism in the inner area of disc gap from the point of view of energy consumption. In this work the inter-fibre refining was studied using equipment for shear and compression. Fibre-to-fibre refining was found to be an effective way to refine fibres from coarse pulp to separated, fibrillated and peeled fibres if frictional forces inside the compressed pulp were high enough. It was proposed that high energy of today’s thermomechanical pulping process could derive from too low frictional forces that heated pulp and evaporated water without any changes in fibre structure. The method to calculate power distribution and results of fibre-to-fibre refining experiments may give ideas for developing today’s thermomechanical pulp refiners’ or for developing totally new energy saving mechanical pulping processes.

<p>The growth and removal of inclusions in stirred ladles hasbeen studied. First, the importance of different growthmechanisms suggested in the literature were studied. Simulationresults from a fundamental model of an induction-stirred ladlehave been used as input in the calculations. Based on thegrowth calculations it was concluded that four of the growthmechanisms need not to be considered since they contribute solittle: i) diffusion of oxygen and aluminum to the inclusionsurface, ii) diffusion coalescence, iii) Brown motioncollision, and iv) laminar shear collision. The majorcontributor to inclusion growth is turbulent collision. Growthdue to Stoke's collisions is also somewhat important if largedifferences among inclusion sizes exist.</p><p>Growth of inclusions in gas stirred ladles was studied usinga similar approach as the one for induction stirred ladles, butwith use of simulation results from a fundamental mathematicalmodel of a gas-stirred ladle. Similarly to what was found inthe case of induction stirring, it was found that turbulentcollisions and Stokes collisions appeared to be the majormechanisms for inclusion growth. The contribution of laminarshear collisions to growth was deemed negligible compared tothat of turbulent collisions.</p><p>For the gas stirred ladle different removal mechanisms werealso studied, based on input data from a mathematical model ofa gas-stirred ladle. It was found that different modelssuggested to predict the inclusion removal due to bubbleflotation gave very different results. Also, all models assumeda spherical shape of the gas bubbles, which was found to beless realistic. Therefore, a new model for inclusion removal byspherical cap bubble flotation was developed. In the newcalculations, the most important mechanisms of inclusionremoval were found to be removal to the top slag and removal bybubble flotation, assuming spherical-cap bubbles and planecontact. When the bubbles were assumed to be spherical,resulting removal rates were lower than when they were assumedto be spherical caps. Based on these results it is concludedthat more research is needed to obtain a better understandingof the importance of bubble flotation on inclusion removal.Experiments are clearly needed to determine which modelconcepts produce predictions in best agreement withcorresponding data from actual steelmaking processes.</p>

Climbing film evaporators are in widespread use in the South African sugar industry, with the vast majority of the local sugar mills currently utilising these evaporators as first effect vessels in multiple effect evaporator sets. However, it is generally considered that the performance of these evaporators has not been maximised, and that improvements could be achieved by proper optimisation of the operating parameters. Unfortunately, very little comprehensive design information has been published in the literature. owing to the complexity of the heat transfer and hydrodynamic interactions in the evaporator tube. Attempts at performance improvement have been hampered by the lack of any theory to explain fully the effects of the operating parameters and physical properties of the feed liquor on the performance of the evaporator. In this study. a mathematical model of the climbing film evaporator system was developed in order to assess the effects of changing operating conditions on evaporator performance, based on as solid a theoretical foundation as cunendy possible. The model was tested against experimental data from a pilot plant climbing film evaporator and this experimental data was used to enhance the accuracy of the model by means of process identification. Because of the complexity of the model and the extensive computational time required for its solution, a simplified evaporator model was also developed, based on Iinearisation of the system of ordinary differential equations describing the climbing film evaporator system. This simplified model was used to predict trends in evaporator behaviour under various operating conditions. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2001.

Five diagrams in pocket.

Submitted in fulfillment of the academic requirements of the degree of Master of Applied Sciences in Chemistry, Durban University of Technology, Chemistry Department, Durban, South Africa, 2016. / Cellulose is a sustainable, abundant biopolymer derived from a variety of living species such as plants, animals, bacteria and some amoebas. An attractive source of cellulose for industrial uses is agricultural waste, as this use does not jeopardize food supplies and improves the local rural economy. Sugarcane bagasse (SCB) is one of the main biomass wastes from sugar production and represents 30–40 wt % of sugar production waste. In 2008, South Africa produced on average 22 million tons of sugar cane each season from 14 sugar mill supply areas which resulted in 7,9 million tons of “waste” bagasse. In this study cellulose nanocrystals were prepared from soda pulped sugarcane bagasse by acid hydrolysis followed by separation using centrifugation, ultrasonication and dialysis. Transmission Electron Microscopy (TEM) images showed nanocrystals of approximately 300 nm in length and 20 nm in width. Thermogravimetric Analysis and Differential Thermogravimetry (TGA and DTG) profiles of FD CNC, MCC and Pulped bagasse all had characteristic onset and decomposition temperatures indicating a change in the structure after chemical treatments. Particle size distribution measurements corroborated with the TEM and FE - SEM results and showed that the majority of the nanocrystals were in the 100 – 300 nm range. Attenuated Total Reflectance – Fourier Transform Infra Red (ATR - FTIR) analysis showed functional group changes as the amorphous regions of the polymer were removed revealing the ordered crystalline portions. These were further confirmed by an increase in the Lateral Orientation Index (LOI) of the samples as the nanocrystals were isolated. X - Ray Diffraction (XRD) Crystallinity Index (CrI) calculations showed a steady increase in the crystallinity of the materials from pulped bagasse to MCC to FD CNC. / M

Magister Curationis - MCur / Background: Service-learning links academic acquisition with community-based work within a partnership framework, which is underpinned by values such as respect, reciprocity, relevance and reflection. This pedagogy has its roots in the northern hemisphere, but has become popular with higher education institutions across the globe. According to Butin, service-learning became institutionalised in the USA after a critical mass of service-learning champions was reached in the 1990s. Hence, the majority of higher education institutions are now subscribing to the national organisation, Campus Compact, which is committed to broadening the footprint of service-learning in this sector. Within the South African higher education sector, “service-learning” as a term became known in 1996. There is, however, wide-spread disagreement as to what is meant by “service-learning”, or exactly what it is meant to accomplish. As a result, education institutions must define it for themselves. A School of Nursing at a university in the Western Cape has defined service-learning during a baseline study that was conducted at the school and this particular definition is, therefore, regarded as a work in progress. Aim: The aim of the study was to refine the preliminary service-learning definition developed during the baseline study by identifying the main concepts that should be included in the definition of service-learning for this School of Nursing.

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering, 2016 / The sulfur removal methods from petroleum products have become an important research topic. Sulfur poisons the catalysts found in vehicles engines and it is also a major air pollutant (Nehlsen, 2005). Recent sulfur specifications require refineries to produce ultra-clean products (Ma et al., 2002). This work aims at exploring a batch adsorptive desulfurization technique using a polymer-supported imidation agent (PI) as an adsorbent. The test was carried out at atmospheric pressure and on two commercial diesel fuels with sulfur contents of 5200 (Case 1) and 670 (Case 2) mg/kg which resembles the feed and outlet streams from the hydrodesulfurization (HDS) reactor respectively. The adsorbent was synthesized according to the procedure described by Shiraishi et al. (2003), BET, FTIR, SEM equipped with EDS and TGA were used for charaterization of the adsorbent. The PI was successfully synthesized and its surface area was 0.5333 m2/g which was incredibly lower than that of the PI synthesized by Fadhel (2010). Hence carbon nanotubes (CNTs) were added to the solution with the aim of improving the sulfur removal efficiency of PI. The obtained results indicated that PI with CNTs yield better results than PI without CNTs. In overall, the lowest sulfur content of 3462 mg/kg (33% removal efficiency) and 26 mg/kg (96% removal efficiency) for Case 1 and Case 2 respectively were obtained. Furthermore, the adsorbents were most effective at lower mixing rates (150 – 400 rpm), longer contact time (30 – 40 hours), practically high adsorbent amount (1 g) and moderate lower temperatures (25 – 50 ºC). The Freundlich adsorption isotherm model was the best fit to the experimental data in both Case 1 and Case 2. The kinetic model that best fitted well the experimental data is the pseudo-second-order model for both Case 1 and Case 2. The kinetic rate constant for Case 2 (4.079 x 10-3g/mg.min) was greater than that for Case 1 (6.75 x 10-5g/mg.min) thus indicating that fuel with low sulfur content has a higher sorption uptake than fuel with high sulfur content. Based on the results obtained in this study, it is suggested that the adsorption of sulfur at high sulfur content fuel is not capable to be used as a complimentary method to the HDS process. On the other hand, at low sulfur content fuel, there is an opportunity for combining this method with the traditional HDS method to achieve ultra-clean fuel. / GR2016

Os modelos moleculares são construídos com base na caracterização da composição do petróleo, que consiste em conhecer informações moleculares detalhadas com o objetivo de identificar os compostos presentes. Este trabalho tem como objetivo construir um banco de dados para a classificação de componentes constituintes de asfaltenos em grupos moleculares. A classificação é feita através da semelhança entre suas massas moleculares em grupos de séries homólogas. Tal classificação é feita por meio da utilização dos dados provenientes da análise de espectrometria de massa e de um algoritmo de busca em linguagem VBA (Visual Basic for Applications), com o objetivo de identificar uma molécula específica em um conjunto de moléculas conhecidas (banco de dados). O método proposto nesse trabalho é baseado na classificação dos compostos através de suas massas moleculares, isto é, os compostos presentes em uma mistura são separados em classes por uma diferença de massa tão pequena quanto se queira. Pode-se, assim, observar a que grupo de moléculas um composto de petróleo pertence por meio de sua massa molecular. Como o banco de dados foi gerado por compostos cuja composição é conhecida, sabe-se que composição um dado composto terá entre as possíveis composições. Para gerar moléculas baseado no conhecimento da composição de petróleo, usam-se as fórmulas gerais dos compostos orgânicos que são formados por séries homólogas. Séries homólogas são séries de compostos orgânicos com propriedades químicas similares cujos componentes diferem entre si por uma massa molecular relativa constante (CH2). Tais séries são geradas e seus pesos moleculares são calculados e armazenados juntamente com suas fórmulas moleculares, em ordem crescente de massa, podendo assim, gerar os grupos moleculares com o auxílio de uma rotina computacional em linguagem VBA. / Molecular models are built based on the characterization of the composition of oil, which consists of detailed molecular information to know in order to identify the compounds present. This work aims to build a database for classifying constituent components of asphaltenes in molecular groups. The classification is done by the similarity of their molecular weights with the use of groups of homologous series. This classification is made by using data from the analysis of mass spectrometry and a search algorithm in language VBA (Visual Basic for Applications) with the aim of identifying a molecule in a specific set of molecules known (database data). The method proposed in that work is based on the classification of the compounds through their molecular weights, i.e., the compounds in a mixture are separated into classes by a mass difference as small as one likes. One can therefore see that the group of molecules from petroleum belongs through its molecular weight. Because the database is generated from compounds whose composition is known, it is known that a given compound composition will have all the possible compositions. To generate molecules based on knowledge of the oil composition, it is used the general formulas of organic compounds which are formed by homologous series. Homologous series are series of organic compounds with similar chemical properties whose components differ by a constant relative molecular mass (CH2). Such series are generated and their molecular weights are calculated and stored together with their molecular formulas, in ascending order of mass, being able to generate the molecular groups with the help of a computing routine in VBA language.

As energias renováveis têm ganhado destaque como possíveis soluções para a questão da matriz energética mundial. Dentre as diferentes alternativas está a energia solar. As células fotovoltaicas são produzidas majoritariamente com silício metálico de alta pureza que é produzido tradicionalmente por um processo químico de alta complexidade e custo. Alternativas vêm sendo desenvolvidas para produção deste material, sendo a rota metalúrgica uma delas. Nesta rota parte-se de um silício de menor pureza e removem-se as impurezas através de operações metalúrgicas. Um dos elementos a serem removidos é o carbono, que está majoritariamente presente precipitado na forma de carboneto de silício (SiC). Visando o estudo da formação da macrossegregação de partículas de SiC em Si, ensaios de solidificação em um forno do tipo Bridgman com diferentes velocidades de extração e diferentes diâmetros de molde foram realizados. Ensaios para verificar o efeito de decantação destas partículas na macrossegregação também foram conduzidos. Nos ensaios de solidificação, os resultados mostram que um aumento da velocidade de extração do molde para fora da região quente do forno resulta em uma estrutura de grãos menos alinhada na direção axial dos lingotes cilíndricos. Adicionalmente, o aumento do diâmetro do lingote também possui um efeito na macroestrutura, dependo da velocidade de extração. A macrossegregação de carbono para o topo do lingote é mais severa quanto menor for a velocidade de extração e maior for a direcionalidade dos grãos. Esta macrossegregação é causada pelo empurramento das partículas de SiC pela interface sólido/líquido. A decantação de partículas de SiC causou macrossegregação de C para a base dos lingotes de Si, porém menos acentuada que aquela observada nos ensaios de solidificação direcional. A alteração do período de tempo reservado no experimento para ocorrência da decantação de uma para seis horas não influenciou significativamente a macrossegregação. Para um mesmo tempo de processo, a solidificação direcional a uma velocidade de extração de 5 µm/s resultou em uma maior macrossegregação de carbono do que aquela observada após decantação, apresentando um maior potencial para a remoção do carbono contido no silício. / Renewable energies have been considered as possible solutions to the world energy matrix issue. Solar energy is one of the alternatives. Photovoltaic cells are mainly made of high purity silicon, which is produced by a complex and costly chemical process. New alternative processes are under development and one of them is the metallurgical route. In this route, a less pure silicon is refined and impurities are removed by metallurgical operations. One of the elements to be removed is carbon, which is mainly present as silicon carbide (SiC). Aiming at an investigation about the macrosegregation of carbon and SiC particles in Si, solidification experiments were conducted in a Bridgman type furnace using different extraction velocities and different mold diameters. Experiments to investigate the effects of settling of SiC particles were also carried out. The results show that the mold extraction velocity plays an important role in the grain macrostructure formation: higher velocities give rise to a less directional grain structure. Additionally, the change in the ingot diameter also has an effect on the macrostructure depending on the extraction velocity. Carbon macrosegregation to the ingot top is more severe for lower mold extraction velocities. This macrosegregation is a result of SiC particles being pushed by the solid/liquid interface to the ingot top. The settling of SiC particles causes carbon macrosegregation to the ingot bottom, but less intense than that observed in the directional solidification experiments at the ingot top. The change of settling times from one to six hours, have no significant effect on the degree of macrosegregation. For equal processing times, directional solidification at a mold extraction rate of 5 µm/s causes more carbon macrosegregation than settling, representing a higher potential alternative for carbon removal from silicon.

Com o intuito de elucidar os efeitos das propriedades físicas e morfológicas na efetividade da sacarificação enzimática das fibras de bagaço de cana-de-açúcar, este trabalho propõe o uso de diferentes métodos de processamento físico-químicos e -mecânicos para a modificação da estrutura da parede celular. Os tratamentos físico-mecânicos, através de fenômenos de fibrilação e delaminação, promovem a abertura estrutural das fibras e aumentam a acessibilidade às enzimas hidrolíticas, porém sem modificar a composição química do material. Para uma compreensão abrangente da ação dos métodos físico-mecânicos propostos nas características estruturais, as fibras de bagaço foram previamente tratadas por métodos físico-químicos - hidrotérmico e organossolve - de modo a obter cinco materiais de diferentes composições químicas. O estudo dos tratamentos físico-mecânicos foi realizado empregando-se equipamentos de diferentes configurações, cujos modos de ação e consequente impacto nas fibras diferem entre si, sendo estes dois tipos de refino - refinador de discos Bauer e moinho Jokro, e um tipo de moagem - moinho criogênico. A variável do refino em moinho Jokro foi o tempo de tratamento, enquanto as variáveis do processamento em refinador de discos foi o tempo de refino e a distância entre os discos. Já as condições da moagem criogênica foram definidas de modo a obter amostras homogêneas do ponto de vista macroscópico. As modificações provocadas na estrutura das fibras foram determinadas a partir das análises das áreas superficiais externa (dimensões das fibras) e interna (porosidade da parede celular), além da organização cristalina das fibrilas celulósicas. Primeiramente, estudou-se de modo detalhado os efeitos dos métodos mecânicos nas propriedades estruturais das amostras de bagaço, interpretando-se como os efeitos primários do refino evoluem de acordo com a severidade e o tipo tratamento empregado a partir das caracterizações dos efeitos secundários. Posteriormente, confrontaram-se os resultados obtidos nas análises físicas e morfológicas com o rendimento de açúcares obtido na hidrólise enzimática. Os resultados permitiram constatar que, enquanto o moinho Jokro promoveu um grande aumento no rendimento de glicose obtido por culminar, simultaneamente, no aumento da estrutura capilar pela intensa fibrilação interna, e da área superficial externa tanto pela formação de elementos finos quanto pela redução das dimensões das fibras por corte, o refinador de discos Bauer levou a uma melhoria menos pronunciada na hidrolisabilidade por resultar no aumento da porosidade, porém sem expressivos corte e fibrilação externa das fibras. Diferentemente, a moagem criogênica promoveu apenas a drástica e heterogênea redução das dimensões das fibras, enquanto não permitiu mudanças significativas na hidrolisabilidade das amostras. Por fim, os valores dos parâmetros estruturais determinados foram analisados pelo método estatístico de componentes principais (PCA) visando quantificar por qual fator cada uma destas características influencia na extensão da hidrólise da celulose do bagaço. A PCA permitiu visualizar que os fatores relacionados à superfície interna da parede celular, como a área de poros acessíveis e a dimensão lateral do cristalito de celulose, são os principais aspectos que regem o rendimento de sacarificação da biomassa lignocelulósica. Os resultados deste estudo permitiram assim a proposta de um modelo de predição do comportamento de hidrólise das amostras de bagaço. / In order to elucidate the effects of the physical and morphological properties on the effectiveness of enzymatic saccharification of sugarcane bagasse fibers, this work proposes different methods of physico-chemical and -mechanical processing to modify the cell wall structure. Through fibrillation and delamination phenomena, physico-mechanical treatments promote the structural opening of the fibers and increase the accessibility to hydrolytic enzymes, but without modifications on the chemical composition of the processed material. For a thorough comprehension about the action of the proposed physico-mechanical methods on the structural characteristics, the bagasse fibers were previously treated by physico-chemical methods - hydrothermal and organosolv - to obtain five materials with different chemical composition. The study of the physico-mechanical treatments was performed by equipment with different configuration, which operating modes and consequent impact on the fibers differ from each other. The equipment were two types of refiner - Bauer discs refiner and Jokro mill - and one type of mill - cryogenic mill. The refining variable considered for the Jokro mill was the refining time, while the processing variables for the disc refiner were the refining time and the discs gap. Concerning the cryogenic mill, the operation conditions were defined to achieve macroscopic homogeneous samples. Modifications on the fibers structure were assessed by analysis of the external and internal surfaces (fibers dimension and the cell wall porosity, respectively), as well as the crystalline organization of the cellulosic fibrils. Firstly, it was performed a thorough study concerning the effects of the mechanical methods in the structural properties of the bagasse samples. In this study, it was interpreted how the primary effects of refining evolve according to severity and type of treatment from the characterization of the secondary effects. Then, the results acquired in the physical and morphological analysis were confronted with the glucose yield obtained in the enzymatic hydrolysis. The results showed that the Jokro mill promoted a great increase in the glucose yield by culminating, simultaneously, in the increase of the capillary structure by the intense internal fibrillation, and of the external surface area both by the formation of fines as by the reduction of the dimensions of fibers by cutting. In turns, the Bauer discs refiner leaded to a lower improvement of the bagasse pulps hydrolysability, which was a consequence of the increased porosity, but without expressive cut and external fibrillation of the fibers. In a different way, the cryogenic milling promoted just a drastic and heterogeneous reduction of the fibers dimensions, without any significant change in the hydrolysability of the samples. Finally, the determined values of the structural parameters were analyzed by the statistical method of the principal component analysis (PCA), aiming to quantify by which factor each one of these characteristics influences in the extent of hydrolysis of bagasse cellulose. The PCA showed that the factors related to the internal surface of the cell wall, such as the accessible pore area and the lateral dimension of the cellulose crystallite, are the main aspects that govern the saccharification yield of the lignocellulosic biomass. The results of this study allowed the proposal of an empiric prediction model of the hydrolysis behavior of the bagasse samples.