The fluid bed granulation is a well-established method how to improve such properties of powders as flowability and increase content uniformity of the tablets. In this thesis, there was evaluated a granulation process on a lab scale fluid Glatt bed granulator and optimized for highest possible yield. Product yield in the size range of 80-90 % of granules and process reproducibility were stated as most effective. The product was analysed for its particle size distribution, the API distribution within the different particle size fractions and the flowability of the final granules. For process optimization, the most critical parameters such as spraying rate, particle size of raw materials and fluid bed pressure were identified and evaluated. As the highest-yielding dosage for the powder binder was found the spraying rate of 9 g/min. Changes in bed fluid pressure and nozzle pressure showed no significant improvement. Different grades of caffeine were compared for their impact on the granulation properties. Sieved caffeine enhanced yield of the product and reproducibility compared to bulk or disagglomerated caffeine.

Due to its prevalence over large, densely populated areas, ammonium nitrate is an important chemical species in aerosol research. However, due to its volatility at ambient temperatures and over low temperature gradients, ammonium nitrate can be a difficult species to accurately measure. The volatility of ammonium nitrate is known to be dependent on temperature, relative humidity, the internal mixing state of the particle, and availability of the precursor gas constituents. The particle's physical state affects the equilibrium constant value of the ammonium nitrate - nitric acid / ammonia exchange and helps determine the dissociation rate. For indoor aerosol research, the outdoor originating aerosol particles' exposure to the new physical conditions indoors, such as changes in temperature, humidity, and particle-surface reactions within the microenvironment all accelerate ammonium nitrate dissociation. This increased rate of partitioning can generate artifacts on datasets, increase indoor particle formation, and accelerate the corrosion of cultural antiquities through acidification. The magnitude of these impacts is uncertain due to the current lack of knowledge on particle transformation processes when outdoor originating particles migrate indoors. To address this gap in knowledge, this thesis...

The separation of solids from biological wastewater treatment is an important step in the treatment process, as it has a significant impact on effluent water quality. The moving bed biofilm reactor (MBBR) technology is a proven upgrade or replacement wastewater treatment system for carbon and nitrogen removal. However, a challenge of this technology is the characteristics of the effluent solids that results in their poor settlement; with settling being the common method of solids removal. The main objective of this research is to understand and expand the current knowledge on the settling characteristics of MBBR produced solids and the parameters that influence them. In particular, in this dissertation, the impacts are studied of carrier types, biofilm thickness restraint design of carriers, and varying carbonaceous loading rates on MBBR performance, biofilm morphology, biofilm thickness, biofilm mass, biofilm density, biofilm detachment rate, solids production, particle size distribution (PSD) and particle settling velocity distribution (PSVD). With this aim, three MBBR reactors housing three different carrier types were operated with varying loading rates. In order to investigate the effect of carrier geometrical properties on the MBBR system, the conventional, cylindrically-shaped, flat AnoxK™ K5 carrier with protected voids was compared to two newly-designed, saddle-shaped Z-carriers with the fully exposed surface area. Moreover, the AnoxK™ Z-200 carrier was compared to the AnoxK™ Z-400 carrier to evaluate the biofilm thickness restraint design of these carriers, where the Z-200 carrier is designed for greater biofilm thickness-restraint. The Z-200 carrier is designed to limit the biofilm thickness to the level of 200 µm as opposed to 400 µm for the Z-400 carrier. Finally, to investigate the effects of varying carbonaceous loading rates on system removal performance, biofilm characteristics and solids characteristics, further analyses were performed at three different loading rates of 1.5 to 2.5 and 6.0 g-sBOD/m2·d in steady-state conditions. The PSD and the PSVD analyses were combined to relate these two properties. A settling velocity distribution analytical method, the ViCAs, was applied in combination with microscopy imaging and micro-flow imaging to investigate the relation of PSD and settling behaviour of MBBR produced particles. The obtained results have indicated that the carrier type significantly impacted the MBBR performance, biofilm, and particle characteristics. As such, the K5 carrier MBBR system demonstrated a statistically significantly higher carbonaceous removal rate and efficiency (3.8 ± 0.3 g-sBOD/m2·d and 59.9 ± 3.0% sBOD removal), higher biofilm thickness (281.1 ± 8.7 μm), higher biofilm mass per carrier (43.9 ± 1.0 mg), lower biofilm density (65.0 ± 1.5 kg/m3), lower biofilm detachment rate (1.7 ± 0.7 g-TSS/ m2·d) and hence lower solids production (0.7 ± 0.3 g-TSS/d) compared to the two Z-carriers. The Z-carriers' different shape exposes the biofilm to additional shear stress, which could explain why the Z-carriers have thinner and denser biofilm, resulting in higher solids production and lower system performance in comparison with K5. Moreover, the carrier type was also observed to impact the particle characteristics significantly. PSD analysis demonstrated a higher percentage of small particles in the Z-carrier system effluent and hence a significantly lower solids settling efficiency. Therefore, the solids produced in the K5 reactor have shown enhanced settling behaviour, consisting of larger particles with faster settling velocities compared to Z-carriers. This dissertation also investigated the effects of restraint biofilm thickness on MBBR performance by comparing the Z-200 biofilm thickness-restraint carrier to the Z-400 carrier. No significant difference was observed in removal efficiency, biofilm morphology, biofilm density, biofilm detachment rate, and solids production between the Z-200 to the Z-400 carriers. The PSD and the PSVD analyses did not illustrate any significant difference in the particles’ settling behaviour for these two biofilm thickness restraint carriers, indicating that the biofilm thickness-restraint carrier design was not a controlling factor in the settling potential of MBBR produced solids. Finally, this research studied the effect of varying loading rates and demonstrated a positive, strong linear correlation between the measured sBOD loading rate and the removal rate, indicating first-order BOD removal kinetics. The biofilm thickness, biofilm density and biofilm mass decreased when the surface area loading rate (SALR) was increased from 2.5 to 6.0 g-sBOD/m2·d. The solids retention time (SRT) was also shown to decrease by increasing the SALR, where the lowest SRT (1.7 ± 0.1 days) was observed at the highest SALR, with the highest cell viability (81.8 ± 1.7%). Significantly higher biofilm detachment rate and yield were observed at SALR 2.5, with the thickest biofilm and a higher percentage of dead cells. Consequently, a higher fraction of larger and rapidly settling particles was observed at SALR of 2.5 g-sBOD/m2·d, which leads to a significantly better settling behaviour of the MBBR effluent solids. This study expands the current knowledge of MBBR-produced particle characteristics and settling behaviour. A comprehensive understanding of the MBBR system performance and the potential influencing factors on the MBBR produced solids, particle characteristics, and their settleability will lead to optimized MBBR design for future pilot- and full-scale applications of the MBBR.

The production of metal powders by water atomisation is a well established process, which can be used to produce a wide range of particle sizes. A careful control of the particle size distribution is necessary, to atomise powders with a high quality and at a low production cost. Therefore, it is necessary to have a substantial knowledge of the relation between operational parameters and the particle size, to be able to produce water atomised metal powders with consistent and high yields. The main purpose with this thesis was to increase the knowledge about factors which affect the mass median particle size (d50) for water atomised metal powders. The specific objectives with the study were to develop a theoretical d50 model and to investigate the relation between the particle size and the physical properties of the liquid metal. Pilot scale experiments for liquid iron showed that alloy additions of carbon and sulphur decreased the d50 value, at a maintained liquid steel temperature before atomisation. Moreover, it was indicated that the reduced particle size at increased %C and %S contents may be related to a decreased viscosity and surface tension of the liquid metal, respectively. An alternative explanation could be that raised superheats at increased carbon contents increased the total available time for atomisation, which may have contributed to a reduction of the d50 value. The theoretical d50 model developed in this work showed a very good correlation to the current experimental data. The model considers the influence of surface tension, viscosity, melt stream diameter, water pressure, water jet angle and water to metal ratio. This model was further used to analyse how the d50 value was influenced by the viscosity and the surface tension. A reduced viscosity from 4∙9 to 2∙1 mPa s decreased the d50 value with 33%. In addition, the particle size was estimated to decrease with 21% by decreasing the surface tension from 1840 to 900 mN m-1. / Q 20120529

Denna licensiatavhandling behandlar oxidativ upplösning av UO2. Upplösning av UO2 studeras huvudsakligen då UO2-matrisen hos använt kärnbränsle förväntas fungera som en barriär mot frigörande av radionuklider i ett framtida djupförvar. Lösligheten av U(IV) är mycket låg under i djupförvaret rådande förhållanden emedan U(VI) har betydligt högre löslighet. Oxidation av UO2-matrisen kommer därför att påverka dess löslighet och därmed dess funktion som barriär. I denna avhandling studeras den relativa effektiviteten av en- och två-elektronoxidanter för upplösning av UO2. Vid låga oxidantkoncentrationer är utbytet för upplösningen för en-elektronoxidanter signifikant lägre än för två-elektronoxidanter. För en-elektronoxidanter ökar dock utbytet med ökande oxidanthalt, vilket kan förklaras av den ökade sannolikheten för två konsekutiva en-elektronoxidationer av samma reaktionssite och den ökade möjligheten till disproportionering. Radikaler och molekylära radiolysprodukters relativa inverkan på oxidativ upplösning av UO2 studeras också i denna avhandling genom mätning av mängden upplöst U(VI) i γ-bestrålade system som dominerades av olika oxidanter. Dessa studier visade att upplösningshastigheten av UO2 kan uppskattas från oxidantkoncentrationer framtagna genom simuleringar av radiolys i motsvarande homogena system och hastighetskonstanterna för ytreaktionerna. Simuleringarna visar att de molekylära oxidanterna kommer vara de viktigaste oxidanterna i alla system i denna studie vid långa bestrålningstider (>10 timmar). Vid liknande simuleringar av α-bestrålade system fanns att vid förhållanden relevanta för ett djupförvar för använt kärnbränsle, är det endast de molekylära oxidanterna (i huvudsak H2O2) som är av betydelse för upplösningen av bränslematrisen. Då använt kärnbränsle innehåller en mängd radionuklider som utsätter UO2-matrisen för kontinuerlig bestrålning, är det av vikt att undersöka hur bestrålning påverkar reaktiviteten av UO2. Bestrålningseffekten på reaktionen mellan UO2 och MnO4- studerades. Dessa försök visade att bestrålning av UO2 vid doser >40 kGy leder till att reaktiviteten ökar upp till 1.3 gånger reaktiviteten av obestrålad UO2. Den ökade reaktiviteten kvarstår efter bestrålningen och effekten kan därför möjligen tillskrivas permanenta förändringar i materialet. Vid uppskattning av reaktiviteten hos använt kärnbränsle måste hänsyn tas till denna effekt då bränslet redan efter ett par dagar i reaktor blivit utsatt för doser >40 kGy. Det har tidigare föreslagits att hastigheten för en heterogen västka/fast-fas reaktion är beroende av partikelstorleken hos det fasta materialet, vilket har studerats för UO2-partiklar i denna avhandling. Experimentellt bestämda kinetiska parametrar jämförs med de föreslagna ekvationerna för fyra storleksfraktioner av UO2-pulver och en UO2-pellet. Studien visade partikelstorleksberoendet av andra ordningens hastighetskonstant och aktiveringsenergin för oxidation av UO2 med MnO4- beskrivs relativt väl av de föreslagna ekvationerna. / The general subject of this thesis is oxidative dissolution of UO2. The dissolution of UO2 is mainly investigated because of the importance of the UO2 matrix of spent nuclear fuel as a barrier against radionuclide release in a future deep repository. U(IV) is extremely insoluble under the reducing conditions prevalent in a deep repository, whereas U(VI) is more soluble. Hence, oxidation of the UO2-matrix will affect its solubility and thereby its function as a barrier. In this thesis the relative efficiency of one- and two electron oxidants in dissolving UO2 is studied. The oxidative dissolution yield of UO2 was found to differ between one- and two-electron oxidants. At low oxidant concentrations the dissolution yields for one-electron oxidants are significantly lower than for two-electron oxidants. However, the dissolution yield for one-electron oxidants increases with increasing oxidant concentration, which could be rationalized by the increased probability for two consecutive one-electron oxidations at the same site and the increased possibility for disproportionation. Furthermore, the relative impact of radical and molecular radiolysis products on oxidative dissolution of UO2 is investigated. Experiments were performed where the amount of dissolved U(VI) was measured in γ-irradiated systems dominated by different oxidants. We have found that the UO2 dissolution rate in systems exposed to γ-irradiation can be estimated from oxidant concentrations derived from simulations of radiolysis in the corresponding homogeneous systems and rate constants for the surface reactions. These simulations show that for all systems studied in this work, the molecular oxidants will be the most important oxidants for long irradiation times (>10 hours). Similar simulations of α-irradiated systems show that in systems relevant for a deep repository for spent nuclear fuel, only the molecular oxidants (mainly H2O2) are of importance for the dissolution of the fuel matrix. The effect on UO2 reactivity by irradiation of the material is of importance when predicting the spent fuel dissolution rate since the fuel, due to its content of radionuclides, is exposed to continuous self-irradiation. The effect of irradiation on the reaction between solid UO2 and MnO4- in aqueous solutions was studied. It was found that irradiation of UO2 at doses >40 kGy increases the reactivity of the material up to ~1.3 times the reactivity of unirradiated UO2. The increased reactivity remains after the irradiation and can possibly be attributed to permanent changes in the material. This issue must be taken into account when predicting the reactivity of spent nuclear fuel since the fuel is exposed to doses >40 kGy after only a few days in the reactor. It has earlier been suggested that the rate of a heterogeneous liquid-solid reaction depends on the size of the solid particles. This was investigated for UO2 particles in this thesis. Experimental kinetic parameters are compared to the previously proposed equations for UO2 powder of four size fractions and a UO2 pellet. We have found that the particle size dependence of the second order rate constant and activation energy for oxidation of UO2 by MnO4- is described quite well by the proposed equations. / QC 20101123

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using the sol-gel technique. The effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were somewhat lower compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin's structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 500-1100 nm except for the W-containing sample obtained with trimethylstearylammonium chloride, which was significantly lower. This unusual effect was attributed to stabilization of primary silica nanoparticles by interactions between the surfactant and HPA. High ratio HPA/TEOS resulted in partial loss of porosity. Obtained results might be used for optimization of synthesis of effective catalysts and adsorbents containing HPAs in mesoporous structure.

This project deals with the mixed micellar and interfacial properties of mixtures of three surfactants [sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and tetraethylene glycol monododecyl ether (C12E4)] with ABA symmetrical triblock copolymer (Pluronic F127), which has many industrial applications. Evidence of F127 micellisation and interaction with surfactants in the aqueous phase is inferred through interfacial tension measurements. The solution containing diluted monomeric F127 showed complex formation with surfactants before the latter self-aggregate as pure micelles. The simultaneous presence of ionic surfactants and micellar F127 in solutions displayed a decrease of interfacial activity and led to the conclusion of F127 micelles disruption. C12E4 was found to interact differently with micellar F127 in forming mixed micelles, and no loss of interfacial activity was recorded. This “association-dissociation” behaviour of F127 and surfactants was leveraged to understand the stability of mineral oil in water emulsions formulated with them in the presence of sodium phosphate (Na3PO4). The mechanisms of emulsions breakdown were found to rely on aggregation behaviour and complex structure of F127 and surfactants mixtures in solution. Laser diffraction showed that unlike SDS and CTAB, mixed-emulsifier systems containing C12E4 are stable to both flocculation, Ostwald ripening and coalescence. Due to electrostatic repulsion between its head group and F127 hydrophilic block, and also because of the combined effect of Ostwald ripening and coalescence, CTAB emulsifier containing systems displayed quicker instability than SDS. SDS containing systems showed a progressive shifting of droplets size distributions to bimodality as SDS concentration was increased and heat exposure pursued, revealing the activity of two distinct population of droplets in the emulsions. More insight on the mechanisms underlying the stability of the three mixed emulsifier systems was gained in performing optical microscopy and rheology measurements; the results were found to be consistent with particle size distribution. / Dissertation (MSc (Applied Science: Chemical Technology))--University of Pretoria, 2020. / Chemical Engineering / MSc (Applied Science: Chemical Technology) / Unrestricted

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19282号 / 工博第4079号 / 新制||工||1629(附属図書館) / 32284 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 中川 一, 教授 藤田 正治, 准教授 川池 健司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21096号 / 工博第4460号 / 新制||工||1693(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 高岡 昌輝, 教授 田中 宏明, 准教授 大下 和徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Particle breakage can be significant in stirred vessels such as crystallizers. During crystallization, particle breakage can occur due to particle contact with other particles, the impeller, the suspension fluid, and/or the vessel. Such breakage produces fines and can cause filter plugging downstream. Although research has been conducted with respect to particle breakage, a comprehensive study is still needed to quantify the breakage occurring in stirred vessels. The overall goal of this research is to model the particle breakage occurring in a stirred vessel by analyzing the particle size and shape distributions that result from breakage. Breakage experiments are based on collision influences that affect the two dominant collisions types, crystal-to-crystal and crystal-to-impeller collisions. Results showed that the quantity of fines produced are affected by the solids concentration or magma density and suspension fluid utilized. Additionally, aqueous saturated solutions produced particle size distributions that differ from those obtained using a nonsolvent. Similar particle size distributions for two different materials (NaCl and KCl) are achieved in the same nonsolvent (acetonitrile) by adjusting the agitation rate using the Zwietering correlation to account for property differences; moreover, the same agitation rate adjustment produced similar distributions for KCl in acetone and acetonitrile which were both nonsolvents. However, modifications to the Zwietering correlation, such as changing the significance of the initial particle size, are proposed before this method of adjustment is deemed accurate. Number-based population modeling of particle breakage is achieved within 1-5% error for NaCl at each agitation rate investigated. Breakage modeling using a discretized population balance equation with Austin's equation for attrition and the power law form of the product function for fragmentation is a viable approach; however, more work is needed to increase the accuracy of this model.