<p> This dissertation describes an investigation into the free radical polymerization of styrene in continuous stirred tank reactors (CSTR's). The aim was to develop a steady state polymerization model which would accurately predict conversion and molecular weight distribution (MWD) up to high conversion. </p> <p> The dissertation is divided into three self-contained parts. Part I describes the testing and development of polymerization kinetics using a single CSTR. The single CSTR model is described. Theoretical and experimental conversions and MWD's are compared and discussed. </p> <p> Part II describes the development of a model for a system of CSTR's. It is based upon the single CSTR model and the kinetics developed in Part I. Theoretical and experimental results for a three reactor system are compared and discussed. </p> <p> Part III describes the development of gel permeation chromatography (GPC) for measuring MWD. Molecular weight and resolution calibration data are presented and discussed. Four methods of chromatogram interpretation that correct for imperfect resolution are compared. </p> / Thesis / Doctor of Philosophy (PhD)

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).

Thesis (DTech (Electrical Engineering))--Cape Peninsula University of Technology, 2016. / Majority of the industrial systems encountered are significantly non-linear in nature, so if they are synthesised and designed by linear methods, then some of salient features characterising of their performance may not be captured. Therefore designing a control system that captures the nonlinearities is important. This research focuses on the control design strategies for the Continuous Stirred Tank Reactor (CSTR) process. To control such a process a careful design strategy is required because of the nonlinearities, loop interaction and the potentially unstable dynamics characterizing the system. In these systems, linear control methods alone may not perform satisfactorily. Three different control design strategies (Dynamic decoupling, Decentralized and Input-output feedback linearization controller) are proposed and implemented .in the Matlab/Simulink platform and the developed strategies are then deployed to the design of distributed automation control system configuration using the IEC 61499 standard based functional block programming language. Twin CAT 3.1 system real-time and Matlab/Simulink (www.mathworks.com) environment are used to test the effectiveness of the models The simulation results from the investigation done between Simulink and TwinCAT 3 software (Beckhoff Automation) platforms in the case of the model transformation and closed loop simulation of the process for the considered cases have shown the suitability and the potentials of merging the Matlab/Simulink control function blocks into the TwinCAT 3.1 function blocks in real-time. The merits derived from such integration imply that the existing software and software components can be re-used. This is in line with one of the IEC 6144 standard requirements such as portability and interoperability. Similarly, the simplification of programming applications is greatly achieved. The investigation has also shown that the integration the of Matlab/Simulink models running in the TwinCAT 3.1 PLC do not need any modification, hence confirming that the TwinCAT 3.1 development platform can be used for the design and implementation of controllers from different platforms. Also, based on the steps required for model transformation the between the Matlab/Simulink to the TwinCAT 3 functional blocks, the algorithms of the control design methodologies developed, simulation results are used to verify the suitability of the controls to find whether the effective set-point tracking control and disturbance effect minimisation for the output variables can be achieved in real-time using the transformed Simulink blocks to the TwinCAT 3 functional blocks, then downloaded to the Beckhoff CX5020 PLC for real-time execution. Good set-point tracking control is achieved for the MIMO closed loop nonlinear CSTR process for the considered cases of the developed control methodologies. Similarly, the effects of disturbances are investigated. TwinCAT functional modules achieved good set-point tracking with these disturbances minimization under all the cases considered.

Enzymes, as nature’s catalysts, show remarkable abilities that can revolutionize the chemical, biotechnological, bioremediation, agricultural and pharmaceutical industries. However, the narrow range of stability of the majority of described biocatalysts limits their use for many applications. To overcome these restrictions, extremozymes derived from microorganisms thriving under harsh conditions can be used. Extremophiles living in high salinity are especially interesting as they operate at low water activity, which is similar to conditions used in standard chemical applications. Because only about 0.1 % of all microorganisms can be cultured, the traditional way of culture-based enzyme function determination needs to be overcome. The rise of high-throughput next-generation-sequencing technologies allows for deep insight into nature’s variety. Single amplified genomes (SAGs) specifically allow for whole genome assemblies from small sample volumes with low cell yields, as are typical for extreme environments. Although these technologies have been available for years, the expected boost in biotechnology has held off. One of the main reasons is the lack of reliable functional annotation of the genomic data, which is caused by the low amount (0.15 %) of experimentally described genes. Here, we present a novel annotation algorithm, designed to annotate the enzymatic function of genomes from microorganisms with low homologies to described microorganisms. The algorithm was established on SAGs from the extreme environment of selected hypersaline Red Sea brine pools with 4.3 M salinity and temperatures up to 68°C. Additionally, a novel consensus pattern for the identification of γ-carbonic anhydrases was created and applied in the algorithm. To verify the annotation, selected genes were expressed in the hypersaline expression system Halobacterium salinarum. This expression system was established and optimized in a continuously stirred tank reactor, leading to substantially increased cell amounts and protein yields. The resulting gene expression products were assessed for function in vivo and/or in vitro. Our functional evaluation of the tested genes confirmed our annotation algorithm. Our developed strategy offers a general guide for using SAGs as a source of scientific and industrial investigations into “microbial dark matter” and may help to develop new catalysts, applicable for novel reactions in green chemistry.

The global demand for food is increasing. Different nutrients are used to increase growth in agriculture and are thus essential for the world ́s food supply. An important and common nutrient is phosphorus. It can be mined, in the form of phosphate, from phosphate rock. The problem is that mining causes environmental problems and phosphate rock is a non-renewable resource. A risk is that phosphorus will become a scarce commodity in about 100 years.  Sewage sludge from wastewater treatment plants (WWTP) is rich in phosphorus. In Sweden and other European countries, a stricter legislation is expected with consideration of an increased recovery of phosphorus from sewage sludge. A ban on the spread of hazardous substances like drug residues and heavy metals from the sludge is also expected. Incineration of the sludge can be done to eliminate hazardous substances and at the same time recover phosphorus and metals. Development of technologies to recover phosphorus from incinerated sewage sludge is therefore topical.  EasyMining is a company that invents new technologies to close nutrient cycles. One of their present projects is about recycling phosphorus, iron, and aluminium from incinerated sewage sludge. Hydrochloric acid (HCl) is used to leach the ash and in the following steps metals and phosphorus are recovered, and heavy metals are removed. Batch experiments have been performed and EasyMining examines the process in a continuous stirred tank reactor (CSTR).  The aim with this project is to compare the batch and continuous process for the ash leaching step. The study was limited to investigate different residence times and liquid to solid ratios (L/S ratios) for the ash leaching step in the CSTR. To accomplish the aim, mainly experimental studies have been performed. A total of 14 runs have been conducted to investigate the continuous process. The residence times 10, 30 and 60 min and the L/S ratios 2.5, 3 and 3.5 ml/g were evaluated. The lab-set up consisted of a peristaltic pump to pump diluted HCl solution, a conveyor belt to dose the ash and a CSTR. The filtrate was analysed for phosphorus, iron, and aluminium with a spectrophotometer. Interpretation of the result was conducted after each run and the data was then compared to previous batch data from within the company. A paired t-test was used to evaluate if there was a significant difference in the mean values between different residence times and L/S ratios.  The result shows that the leching is very fast and longer residence times or higher L/S ratios do not result in higher yields for phosphorus, iron, or aluminium. There is no significant difference between the examined residence times or L/S ratios in the paired t-test. Data from the batch process shows that the investigated residence times and L/S ratios do not affect the yield. A more even distribution of the yields is obtained in the batch process compared to the continuous process. The less even distribution in the continuous process, probably depends on errors in the method and the equipment used in the process. For example, there were some problems with the ash dosing, which led to an inconstant L/S ratio in the runs. This affected the calculated yields significantly. Overall, the batch process results in slightly higher yields. This is especially the case when excluding high calculated yields in the continuous process, probably obtained because of an overdosing of the ash. / Den globala efterfrågan på mat ökar. Olika näringsämnen används för att få en högre tillväxt i jordbruket och dessa är essentiella för världens livsmedelsproduktion. Ett viktigt och vanligt näringsämne är fosfor och det bryts i form av fosfat från fosfatmineral. Problemet är att brytningen förorenar miljön och dessutom är fosfat-sten en icke förnyelsebar resurs. Det finns en risk att fosfor blir en bristvara om cirka 100 år.  Avloppsslam från vattenreningsverk innehåller höga fosfatkoncentrationer. I Sverige samt i andra europeiska länder förväntas en striktare lagstiftning, som kräver en ökad återvinningsgrad av fosfor från avloppsslam. Även ett förbud mot spridningen av giftiga substanser som läkemedelsrester och tungmetaller förväntas införas. Slammet kan förbrännas för att eliminera farliga substanser samtidigt som fosfor och olika metaller kan återvinnas. Utvecklingen av nya tekniker för återvinning av fosfor från bränt avloppsslam är därför väldigt aktuell.  EasyMining är ett innovationsföretag som utvecklar nya tekniker för att erhålla slutna näringskretslopp. Ett av deras pågående projekt handlar om att återvinna fosfor, aluminium och järn från förbränt avloppsslam. Saltsyra används för att laka askan och i nästkommande steg återvinns fosfor och metaller, samtidigt som tungmetaller separeras. Satsvisa försök har genomförts och EasyMining vill nu undersöka processen i en tankreaktor.  Syftet med projektet är att jämföra resultat från den satsvisa driften med resultat från en kontinuerlig process för ask-lakningssteget. Studien begränsades till att endast undersöka olika uppehållstider och förhållandet mellan vätskan och askan (L/S-förhållande) i lakningssteget. För att uppnå syftet genomfördes huvudsakligen experimentella studier. 14 körningar genomfördes totalt för undersökning av den kontinuerliga processen. Undersökta uppehållstider var 10, 30 och 60 min och undersökta L/S-förhållandena var 2,5, 3 och 3,5 ml/g. Laborationsuppställningen bestod av en peristaltisk pump för tillförsel av utspädd saltsyralösning, ett rullband för dosering av askan samt en tankreaktor. Filtratet analyserades för fosfor, järn och aluminium i en spektrofotometer. Efter varje körning tolkades resultatet och jämfördes därefter med data från de av företaget tidigare utförda satsvisa försöken. Ett parat t-test användes för att utvärdera om det fanns någon signifikant skillnad i medelvärden mellan olika uppehållstider och L/S-förhållanden.  Resultatet visar att lakningen är väldigt snabb och längre uppehållstider eller högre L/S-förhållanden ger inte högre utbyten för fosfor, järn eller aluminium. Ingen signifikant skillnad erhålls mellan undersökta uppehållstider eller L/S-förhållanden i de parade t-testen. Data från de satsvisa försöken visar att de undersökta uppehållstiderna och L/S-förhållandena inte påverkar utbytet. En mindre spridning av utbyten erhålls i den satsvisa driften jämfört med den kontinuerliga. Den större spridningen i den kontinuerliga processen beror förmodligen på felkällor i processens metod/utrustning. Exempelvis var det en del problem med askdoseringen, vilket medförde icke konstanta L/S-förhållanden. Detta påverkade det beräknade utbytet signifikant. Generellt erhålls något högre utbyten i den satsvisa processen. Framförallt då höga beräknade utbyten exkluderas i den kontinuerliga processen på grund av en överdosering av askan.

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).

In der vorliegenden Arbeit wird die Konzeptionierung und die Realisierung eines teilkontinuierlichen Thermolyseverfahrens zur rohstofflichen Verwertung von Polyethylen- und Polypropylenabfällen beschrieben. Die Ausführung in der zweistufigen Rührkesselkaskade gewährleistete dabei die Trennung der Prozessschritte Schmelzen sowie Cracken der Einsatzmaterialien, woraus ein Thermolyseöl hervorging, welches weitestgehend frei von den Verunreinigungen aus den Abfällen war. Das Thermolyseöl wies eine Zusammensetzung aus Benzin- und Dieselkomponenten auf und erfüllte einige entscheidende Kraftstoffkriterien. Zur Senkung der qualitätsmindernden Olefingehalte wurden in einem weiteren Teil dieser Arbeit Untersuchungen zur heterogen-katalysierten Hydrierung der Siedeschnitte im Schüttgutreaktor und im Rührautoklav durchgeführt. Dabei konnten die Olefingehalte durch den Einsatz eines Palladium-Platin-Trägerkatalysators sowie durch einen Nickel-Gerüstkatalysator maßgeblich gesenkt werden. Als unerwünschtes Nebenprodukt des Thermolyseprozesses resultierte ein geringer Anteil Koks, welcher in der Schmelze akkumulierte und sich teilweise an der Reaktorwand ablagerte. Die entstandenen Mengen wiesen eine Abhängigkeit von der Prozesstemperatur und -dauer auf und mussten aus dem Prozess geschleust werden. Als weitere Nebenprodukte traten ein leichtflüchtiges Spaltgas sowie ein Sumpfrückstand auf. Darüber hinaus wurde gezeigt, dass die aufzuwendende Energie für den Thermolyseprozess durch die Energiegehalte der Nebenprodukte gedeckt werden kann. Neben dem Einsatz als Kraftstoff empfahl sich das Thermolyseöl aufgrund seiner physikalischen und chemischen Eigenschaften gerade im Hinblick auf einen nachhaltigen Umgang mit Ressourcen als beachtenswerter Ersatz für fossiles Rohöl.

L(+)-Lactic acid is a commonly occurring organic acid, which is valuable due to its wide use in food and food-related industries, and its potential for the production of biodegradable and biocompatible polylactate polymers. The aim of this study was to optimize and scale-up a biotechnological process of L(+)-lactic acid production by suspended cells of R. arrhizus DAR 36017 with waste potato starch as the substrate. Commonly used inorganic and organic nitrogen sources, including ammonium sulphate, ammonium nitrate, urea, yeast extract and peptone, were assessed in conjunction with various ratios of carbon to nitrogen (C:N). Fermentation media with a low C:N ratio enhanced the production of lactic acid, biomass and ethanol, while a high C:N ratio led to production of more fumaric acid as a by-product. The use of organic nitrogen sources (yeast extract, peptone and urea) resulted in a significant reduction of lactic acid yields by 15% - 34% with a decrease of C:N from 168 to 28. The use of inorganic nitrogen sources (ammonium nitrate and ammonium sulphate) led to a high lactic acid yield of 84% - 91% at a C:N below 168. Therefore, ammonium nitrate and ammonium sulphate were considered to be better nitrogen sources for lactic acid production. Small pellets are the favoured morphological form for many fermentation processes by filamentous fungi. However, to control filamentous Rhizopus sp in the pellet form in a submerged fermentation system is difficult due to its filamentous characteristics. An acidadapted preculture technique was developed to induce the formation of the pellet form in bioreactors. Using the acid-adapted precultures, the fungal biomass can be controlled in small dispersed pellets as a dominant morphological form. With these small pellets, a lactic acid yield of 86-89%, corresponding to a concentration of 86-89g/L, was obtained in a laboratory scale process using a stirred tank reactor (STR) and a bubble column reactor (BCR). A batch bioprocess for lactic acid production was successfully scaled-up from shake flasks to laboratory scale bioreactors. Results from a simulated scale-up process revealed that the concentration and productivity of lactic acid decreased with the increase of the scale-up steps because of increased pellet size. This suggested that a one-step scale-up process using the acid-adapted preculture may be feasible in an industrial-scale bioreactor system. A comprehensive investigation of the impact of cultivation parameters on the morphology of R. arrhizus and lactic acid production was carried out in the BCR. The results showed that the fungal morphology was significantly influenced by carbon sources, pH, starch concentrations, sparger designs and aeration rates. The favoured morphology for lactic acid production was freely dispersed small pellets, which could be retained as a dominant morphology under operation conditions at pH 5.0 – 6.0, starch concentrations of 60 – 120 g/L and aeration rates of 0.2 – 0.8 vvm, using a sintered stainless steel disc sparger. The optimal cultivation conditions at pH 6.0 and aeration rate of 0.4 vvm resulted in the formation of the freely dispersed small pellets and production of 103.8 g/L lactic acid, with a yield of 87%, from 120 g/L liquefied potato starch in 48 h. This study shows a technically feasible and economically promising process for the production of lactic acid from waste potato starch. The use of waste potato starch instead of pure glucose or starch as substrate can significantly reduce the production cost, making this technology environmentally and economically attractive. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1339122 / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2008