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This thesis provides a detailed evaluation of different environmentally friendly dispersants in invert-emulsion drilling fluids that can be used to drill wells under difficult conditions such as HPHT. The drilling fluid is weighted by manganese tetraoxide (Mn3O4) particles, which have a specific gravity of 4.8 and a mean particle diameter of ca1 micrometers. Manganese tetraoxide has different wetting properties and surface chemistry than other weighting agents. Hence, there is a need to find dispersants for manganese tetraoxide that give reduced sag, reduced rheology, and low fluid-loss at HPHT conditions. This is particularly important for deep wells with narrow operating windows between pore-pressure and fracture pressure gradients. The stricter global environmental regulations mandated the dispersants to be environmentally friendly, e.g. within OCNS group D or E. First, oil compatibility tests and particle settling time experiments were conducted on 31 dispersants. From the experiments, we identified 3 oil-compatible dispersants that gave the longest settling time in base oil and belonged to OCNS group D. We investigated the effectiveness of selected chemicals in dispersing manganese tetraoxide at HPHT conditions. 1.95 and 2.4 S.G. drilling fluid samples were first prepared and tested without any contaminant and then in the presence of rev dust and cement as contaminants. Drilling fluid samples were statically aged at 400 degrees F and 500 psi for 16 hours. Sag and rheological measurements were taken before and after aging to determine the effect of HPHT conditions on fluid properties. Then, HPHT dynamic filtration tests were done at 500 psi differential pressure and 300 degrees F to determine HPHT dynamic fluid-loss. We have found that one of the dispersants (nonionic) gives low rheology and reduced sag before and after static aging. It also gives the lowest fluid-loss of the selected dispersants. For 2.4 S.G. fluid without contaminants, 10-minute gel strength was reduced from 50 to 32 lb/100 ft^2, plastic viscosity from 37 to 25 cp, sag from 0.249 to 0.135 lbm/gal, and fluid-loss was reduced from 44.4 to 39.6 cm^3 with the addition of dispersant. This dispersant prevents agglomeration of particles, thereby reducing fluid rheology, sag, and fluid-loss.

Invert syrup is a liquid sweetener, which is produced by sucrose hydrolysis to form fructose and glucose. Important qualitative parameter of invert syrup is the sucrose inversion – weight percentage of invert sugar (sum of fructose and glucose) in invert syrup dry mass. This diploma thesis presents a possibility of sucrose inversion determination by polarimetry in combination with refractometry in invert syrups of 70–78 % dry mass produced at 80 °C and pH 2,4. New relationship describing the sucrose inversion as a function of polarization and refractometric dry mass was determined. The results of sucrose inversion determined using this new relationship were compared to results obtained by HPLC/RI, which was used as a reference method. The difference between these 2 determination methods was 0,1 ± 0,5 %. The new relationship was detemined with reference to the fact, that under the processing conditions, more glucose than fructose is formed. The fructose : glucose concentration ratio formed under processing conditions was observed to be equal 0,96 ± 0,02.

Fruto-oligossacarídeos (FOS) são fibras prebióticas com poder adoçante considerável, sendo um produto de alto valor para a indústria de alimentos. Açúcar invertido é o produto da hidrólise da sacarose possuindo maior poder adoçante, menor susceptibilidade à cristalização e maior higroscopicidade com relação à sacarose, sendo de grande interesse industrial. Ambos produtos podem ser produzidos por reações enzimáticas, utilizando β-frutosiltransferase e β- frutofuranosidase respectivamente, no entanto processos enzimáticos costumam ser caros devido ao alto custo e baixa estabilidade de enzimas. Esses fatores podem ser contornados com a imobilização da enzima, permitindo a reutilização e por vezes aumentando a estabilidade. No presente trabalho a enzima β-frutosiltransferase proveniente de um extrato comercial de Aspergillus aculeatus (Viscozyme L) foi parcialmente purificada, com resina de troca iônica, imobilizada covalentemente em esferas de quitosana e utilizada na produção de FOS. O processo de purificação aumentou a atividade específica em 6 vezes. A estabilidade do biocatalisador imobilizado foi avaliada em 50 bateladas para produção de FOS, foi observado cerca de 55 % de rendimento em cada batelada, sem perda de atividade detectada após as utilizações. Após esse experimento foi testada a utilização das esferas em reatores contínuos com leito fixo e fluidizado, com rendimentos de 59 % e 54 % respectivamente. A produção de açúcar invertido foi feita utilizando a enzima Maxinvert L (β-frutofuranosidase de Saccharomyces cerevisiae) que foi imobilizada, da mesma forma, em esferas de quitosana e sua utilização foi testada em reatores de leito fixo e fluidizado com rendimentos de 98 % e 94 % respectivamente. Os reatores de leito fixo possuem potencial para estudos envolvendo aplicações industriais tanto para produção de FOS quanto para produção de Açúcar Invertido. / Fructooligosaccharides (FOS) are prebiotic fibre with sweetening power, being a highvalue product for the food industry. Invert sugar is the product of sucrose hydrolysis; it has a higher sweetening power, it is less susceptible to crystallization and has a higher hygroscopicity than regular sugar. Finding many uses in food industry processes. Both products can be obtained by enzymatic reactions using β-fructosyltransferase and β- fructofuranosidase, respectively. However, enzymatic processes are often costly because of high enzymatic cost and lack of operational stability. These drawbacks can be overcome by immobilization of enzyme, enabling reuses and usually increasing its stability. In the present work, β-fructofuranosidase from a commercial preparation from Aspergillus aculeatus (Viscozyme L) was partially purified, covalently immobilized on chitosan spheres and used for FOS production. Partial purification resulted in a 6-fold increase in specific activity. Operational stability of biocatalyst was evaluated along 50 batches, resulting in around 55 % yield on each batch and no loss of activity after batches. The immobilized biocatalyst was also used for FOS production in packed bed and fluidized bed reactors with yields of 59 % and 54 % respectively. Invert sugar production was carried out using Maxinvert L (β- fructofuranosidase from Saccharomyces cerevisiae) immobilized, by the same method, on chitosan spheres. Its application on packed bed and fluidized bed reactors was evaluated resulting in yields of 98 % and 94 % respectively. The packed bed reactors presented potential for further studies aiming industrial applications for FOS and Invert Sugar production.

Fruto-oligossacarídeos (FOS) são fibras prebióticas com poder adoçante considerável, sendo um produto de alto valor para a indústria de alimentos. Açúcar invertido é o produto da hidrólise da sacarose possuindo maior poder adoçante, menor susceptibilidade à cristalização e maior higroscopicidade com relação à sacarose, sendo de grande interesse industrial. Ambos produtos podem ser produzidos por reações enzimáticas, utilizando β-frutosiltransferase e β- frutofuranosidase respectivamente, no entanto processos enzimáticos costumam ser caros devido ao alto custo e baixa estabilidade de enzimas. Esses fatores podem ser contornados com a imobilização da enzima, permitindo a reutilização e por vezes aumentando a estabilidade. No presente trabalho a enzima β-frutosiltransferase proveniente de um extrato comercial de Aspergillus aculeatus (Viscozyme L) foi parcialmente purificada, com resina de troca iônica, imobilizada covalentemente em esferas de quitosana e utilizada na produção de FOS. O processo de purificação aumentou a atividade específica em 6 vezes. A estabilidade do biocatalisador imobilizado foi avaliada em 50 bateladas para produção de FOS, foi observado cerca de 55 % de rendimento em cada batelada, sem perda de atividade detectada após as utilizações. Após esse experimento foi testada a utilização das esferas em reatores contínuos com leito fixo e fluidizado, com rendimentos de 59 % e 54 % respectivamente. A produção de açúcar invertido foi feita utilizando a enzima Maxinvert L (β-frutofuranosidase de Saccharomyces cerevisiae) que foi imobilizada, da mesma forma, em esferas de quitosana e sua utilização foi testada em reatores de leito fixo e fluidizado com rendimentos de 98 % e 94 % respectivamente. Os reatores de leito fixo possuem potencial para estudos envolvendo aplicações industriais tanto para produção de FOS quanto para produção de Açúcar Invertido. / Fructooligosaccharides (FOS) are prebiotic fibre with sweetening power, being a highvalue product for the food industry. Invert sugar is the product of sucrose hydrolysis; it has a higher sweetening power, it is less susceptible to crystallization and has a higher hygroscopicity than regular sugar. Finding many uses in food industry processes. Both products can be obtained by enzymatic reactions using β-fructosyltransferase and β- fructofuranosidase, respectively. However, enzymatic processes are often costly because of high enzymatic cost and lack of operational stability. These drawbacks can be overcome by immobilization of enzyme, enabling reuses and usually increasing its stability. In the present work, β-fructofuranosidase from a commercial preparation from Aspergillus aculeatus (Viscozyme L) was partially purified, covalently immobilized on chitosan spheres and used for FOS production. Partial purification resulted in a 6-fold increase in specific activity. Operational stability of biocatalyst was evaluated along 50 batches, resulting in around 55 % yield on each batch and no loss of activity after batches. The immobilized biocatalyst was also used for FOS production in packed bed and fluidized bed reactors with yields of 59 % and 54 % respectively. Invert sugar production was carried out using Maxinvert L (β- fructofuranosidase from Saccharomyces cerevisiae) immobilized, by the same method, on chitosan spheres. Its application on packed bed and fluidized bed reactors was evaluated resulting in yields of 98 % and 94 % respectively. The packed bed reactors presented potential for further studies aiming industrial applications for FOS and Invert Sugar production.

Fruto-oligossacarídeos (FOS) são fibras prebióticas com poder adoçante considerável, sendo um produto de alto valor para a indústria de alimentos. Açúcar invertido é o produto da hidrólise da sacarose possuindo maior poder adoçante, menor susceptibilidade à cristalização e maior higroscopicidade com relação à sacarose, sendo de grande interesse industrial. Ambos produtos podem ser produzidos por reações enzimáticas, utilizando β-frutosiltransferase e β- frutofuranosidase respectivamente, no entanto processos enzimáticos costumam ser caros devido ao alto custo e baixa estabilidade de enzimas. Esses fatores podem ser contornados com a imobilização da enzima, permitindo a reutilização e por vezes aumentando a estabilidade. No presente trabalho a enzima β-frutosiltransferase proveniente de um extrato comercial de Aspergillus aculeatus (Viscozyme L) foi parcialmente purificada, com resina de troca iônica, imobilizada covalentemente em esferas de quitosana e utilizada na produção de FOS. O processo de purificação aumentou a atividade específica em 6 vezes. A estabilidade do biocatalisador imobilizado foi avaliada em 50 bateladas para produção de FOS, foi observado cerca de 55 % de rendimento em cada batelada, sem perda de atividade detectada após as utilizações. Após esse experimento foi testada a utilização das esferas em reatores contínuos com leito fixo e fluidizado, com rendimentos de 59 % e 54 % respectivamente. A produção de açúcar invertido foi feita utilizando a enzima Maxinvert L (β-frutofuranosidase de Saccharomyces cerevisiae) que foi imobilizada, da mesma forma, em esferas de quitosana e sua utilização foi testada em reatores de leito fixo e fluidizado com rendimentos de 98 % e 94 % respectivamente. Os reatores de leito fixo possuem potencial para estudos envolvendo aplicações industriais tanto para produção de FOS quanto para produção de Açúcar Invertido. / Fructooligosaccharides (FOS) are prebiotic fibre with sweetening power, being a highvalue product for the food industry. Invert sugar is the product of sucrose hydrolysis; it has a higher sweetening power, it is less susceptible to crystallization and has a higher hygroscopicity than regular sugar. Finding many uses in food industry processes. Both products can be obtained by enzymatic reactions using β-fructosyltransferase and β- fructofuranosidase, respectively. However, enzymatic processes are often costly because of high enzymatic cost and lack of operational stability. These drawbacks can be overcome by immobilization of enzyme, enabling reuses and usually increasing its stability. In the present work, β-fructofuranosidase from a commercial preparation from Aspergillus aculeatus (Viscozyme L) was partially purified, covalently immobilized on chitosan spheres and used for FOS production. Partial purification resulted in a 6-fold increase in specific activity. Operational stability of biocatalyst was evaluated along 50 batches, resulting in around 55 % yield on each batch and no loss of activity after batches. The immobilized biocatalyst was also used for FOS production in packed bed and fluidized bed reactors with yields of 59 % and 54 % respectively. Invert sugar production was carried out using Maxinvert L (β- fructofuranosidase from Saccharomyces cerevisiae) immobilized, by the same method, on chitosan spheres. Its application on packed bed and fluidized bed reactors was evaluated resulting in yields of 98 % and 94 % respectively. The packed bed reactors presented potential for further studies aiming industrial applications for FOS and Invert Sugar production.

Yes / The performance of buried rigid pipes underneath geogrid-reinforced soil while applying incrementally increased cyclic loading was assessed using a fully instrumented laboratory rig. The influence of varying two parameters of practical importance was investigated; the pipe burial depth and the number of geogrid-layers. Measurements were taken for pipe deformation, footing settlement, strain in pipe and reinforcing layers, and pressure/soil stress on the pipe crown during various stages of cyclic loading. The research outcomes demonstrated a rapid increase in the rate of deformation of the pipe and the footing, and the rate of generated strain in the pipe and the geogrid-layers during the first 300 cycles. While applying further cycles, those rates were significantly decreased. Increasing the pipe burial depth and number of geogrid-layers resulted in reductions in the footing and the pipe deformations, the pressure on pipe crown, and the pipe strains. Redistribution of stresses, due to the inclusion of reinforcing layers, formed a confined zone surrounding the pipe providing it with additional lateral support. The pipe invert experienced a rebound, which was found to be dependent on pressure around the pipe and the degree of densification of the bedding layer. Data for strains measured in the geogrid-layers showed that despite the applied loading value and the pipe burial depth, the tensile strain in the lower geogrid-layer was usually higher than that measured in the upper layer.

An investigation was done into the recovery of invert sugar from sugar cane molasses. A pilot plant was designed and constructed to evaluate the clarification and separation of molasses to produce invert sugar syrup. The aim of the pilot plant was to prove the process and deliver data so as to facilitate the design and prove the financial viability of a commercial plant. The pilot plant had to process 300 kg/day of molasses. The clarification of molasses by centrifugal separation, a known desludging process, did not produce a product of acceptable quality which could be used in a chromatographic separator. The results were disappointing. The product obtained was also not suitable for dead end pressure filtration. The turbidity remaining after the centrifugal separation also did not respond to a second flocculation process. Conventional settling clarification was investigated. Seven factors that could influence the consolidation and settling of suspended solids in molasses were identified, namely: the age of the diluted molasses, the temperature of the flocculated mixture, the variations across various batches of flocculant, the effect of reaction time of the phosphoric acid, the optimum flocculant dosing concentration, the optimum concentration of the molasses solution and the effect of increasing the acid dosage. The optimum conditions to clarify molasses through settling were found to be: fresh molasses, at 28 Brix and 60°C, allowing 10 min intervals between acidification with 3,75 g (as 100%) phosphoric acid/ kg dry material (assumed equal to Brix) and neutralisation with 5 g (as 100%) caustic/kg dry material (assumed equal to Brix), flocculation with any batch of flocculant 6195, dosed as a 1000 ppm solution. Commercial equipment was evaluated. The pilot plant E-cat clarifier was operated at 300 l/h and a thick sludge formed. The overflow was clear and it could be filtered. The molasses obtained was suitable for chromatographic separation. The recovery of sugars from molasses sludge has economic merit. From the evaluation of centrifugal separation and gravity separation it is clear that gravity separation again is the best method. The sweet-water obtained is consistent within the clarity requirement of 10 NTU/Brix and can be used to dilute raw molasses in the upstream processing step. The clarification process that was developed is patented. [Bekker, Stolz et.al. (2001)] A sugar recovery of 93.9 mass % at a purity of 99.7 mass % from molasses, was achieved using a simulated moving bed, ion exclusion, pilot plant. The operating conditions for this performance were: feed flow at 14 l/h and at a temperature above 60 °C; water flow at 63 l/h and at a temperature above 65 °C; extract flow at 21 l/h; raffinate flow at 56 l/h; loop flow at 78 l/h and step time at 1326 seconds. This relates to the following bed volumes of the various separation zones: Bed Volume Zone 1 = 0.694; Bed Volume Zone 2 = 0.591; Bed Volume Zone 3 = 0.661; Bed Volume Zone 4 = 0.383. There is a trade-off between purity and recovery and a reduction in water usage. A preliminary environmental impact assessment and conceptual mass balance were done. The proposed plant integrates well into the existing Komati Mill of TSB and does not pose any significant environmental threat. The plant requires certain services from the mill. The mass balance investigated the water and steam consumption of the plant. Process integration was done so as to obtain the optimum utility consumption. The utility consumption of the plant does not exceed the capacity available at the mill. A small boiler is however required to produce steam during the annual mill maintenance period. Various techniques were used in a cost estimation for the invert sugar plant. The internal rate of return (IRR) is 42% for a fixed capital investment of R94,270,000.00. The net return rate (NRR) for the project is 4%/year, the net present value (NPV) - discounted at a 30% cost-of-capital is R41,782,000.00. The net payout time (NPT) is 5.207 years. The project fulfils the financial requirements set by TSB. It is now possible and viable to desugarize cane molasses.

The SHIRA method of Mehrmann and Watkins belongs among the structure preserving Krylov subspace methods for solving skew-Hamiltonian eigenvalue problems. It can also be applied to Hamiltonian eigenproblems by considering a suitable transformation. Structure induced shift-and-invert techniques are employed to steer the algorithm towards the interesting region of the spectrum. However, the shift cannot be altered in the middle of the computation without discarding the information that has been accumulated so far. This paper shows how SHIRA can be combined with ideas from Ruhe's Rational Krylov algorithm to yield a method that permits an adjustment of shift after every step of the computation, adding greatly to the flexibility of the algorithm. We call this new method rational SHIRA. A numerical example is presented to demonstrate its efficiency.

Real numbers are usually represented by various discrete objects such as floating points or partial decimal expansions. This is mainly because the clas- sical computability theory relates to computers which work with discrete data. Nevertheless, for theoretical purposes it is interesting to look at models of com- putation that deal with real numbers as with objects of unit size. A very natural such model was suggested by Blum, Shub and Smale in 1989. In 2012 Grigoriev and Nikolenko studied various cryptographic tasks involv- ing real numbers (for example, biometric authentication) and they considered the BSS machine model. In this work we focus on hard to invert functions in this model of computation. Our main theme is to analyse whether there are real functions of one variable that are easier to compute than to invert by a BSS machine. 1