Submitted in fulfillment of the requirements for the degree of Doctor of Philosophy: Biotechnology, Durban University of Technology, Durban, South Africa, 2017. / Fossil carbon dioxide emissions can be biologically fixed which could lead to the development of technologies that are both economically and environmentally friendly. Carbon dioxide, which is the basis for the formation of complex sugars by green plants and microalgae through photosynthesis, has been shown to significantly increase the growth rates of certain microalgal species. Microalgae possess a greater capacity to fix CO2 compared to terrestrial plants. Selection of appropriate microalgal strains is based on the CO2 fixation and tolerance capability, both of which are a function of biomass productivity. Microalgal biomass could thus represent a natural sink for carbon. Furthermore, such systems could minimise capital and operating costs, complexity, and energy required to transport CO2 to other places. Prior to the development of an effective CO2 mitigation process, an essential step should be to identify the most CO2-tolerant indigenous strains. The first phase of this study therefore focused on the isolation, identification and screening of carboxyphilic microalgal strains (indigenous to the KwaZulu-Natal province in South Africa). In order to identify a high carbon-sequestering microalgal strain, the physiological effect of different concentrations of carbon sources on microalgae growth was investigated. Five indigenous strains (I-1, I-2, I-3, I-4 and I-5) and a reference strain (I-0: Coccolithus pelagicus 913/3) were subjected to CO2 concentrations of 0.03 - 15% and NaHCO3 of 0.05 - 2 g/1. The logistic model was applied for data fitting, as well as for estimation of the maximum growth rate (µmax) and the biomass carrying capacity (Bmax). Amongst the five indigenous strains, I-3 was similar to the reference strain with regards to biomass production values. The Bmax of I-3 significantly increased from 0.214 to 0.828 g/l when the CO2 concentration was increased from 0.03 to 15% (r = 0.955, p = 0.012). Additionally, the Bmax of I-3 increased with increasing NaHCO3 concentrations (r = 0.885, p = 0.046) and was recorded at 0.153 g/l (at 0.05 g/l) and 0.774 g/l (at 2 g/l). Relative electron transport rate (rETR) and maximum quantum yield (Fv/Fm) were also applied to assess the impact of elevated carbon sources on the microalgal cells at the physiological level. Isolate I-3 displayed the highest rETR confirming its tolerance to higher quantities of carbon. Additionally, the decline in Fv/Fm with increasing carbon was similar for strains I-3 and the reference strain (I-0). Based on partial 28S ribosomal DNA gene sequencing, strain I-3 was found to be homologous to the ribosomal genes of Chlorella sp. The influence of abiotic parameters (light intensity and light:dark cycles) and varying nutrient concentrations on the growth of the highly CO2 tolerant Chlorella sp. was thereafter investigated. It was found that an increase in light intensity from 40 to 175 umol m2 s-1 resulted in an enhancement of Bmax from 0.594 to 1.762 g/l, respectively (r = 0.9921, p = 0.0079). Furthermore, the highest Bmax of 2.514 g/l was detected at a light:dark cycle of 16:8. Media components were optimised using fractional factorial experiments which eventually culminated in a central composite optimisation experiment. An eight-factor resolution IV fractional factorial had a biomass production of 2.99 g/l. The largest positive responses (favourable effects on biomass production) were observed for individual factors X2 (NaNO3), X3 (NaH2PO4) and X6 (Fe-EDTA). Thereafter, a three-factor (NaNO3, NaH2PO4 and Fe-EDTA) central composite experimental design predicted a maximum biomass production of 3.051 g/l, which was 134.65% higher when compared to cultivation using the original ASW medium (1.290 g/l). A pilot scale flat panel photobioreactor was designed and constructed to demonstrate the process viability of utilising a synthetic flue gas mixture for the growth of microalgae. The novelty of this aspect of the study lies in the fact that a very high CO2 concentration (30%) formed part of the synthetic flue gas mixture. Overall, results demonstrated that the Chlorella sp. was able to grow well in a closed flat panel reactor under conditions of flue gas aeration. Biomass yield, however, was greatly dependent on culture conditions and the mode of flue gas supply. In comparison to the other batch runs, run B yielded the highest biomass value (3.415 g/l) and CO2 uptake rate (0.7971 g/day). During this run, not only was the Chlorella strain grown under optimised nutrient and environmental conditions, but the culture was also intermittently exposed to the flue gas mixture. Results from this study demonstrate that flue gas from industrial sources could be directly introduced to the indigenous Chlorella strain to potentially produce algal biomass while efficiently capturing and utilising CO2 from the flue gas. / D

Abstract Non-linear methods have been utilised in modelling the processes on a flue-gas oxygen-content control system of a power plant. The ultimate objective is to reduce NOx and CO emissions by enhancing the control system. By investigating the flue-gas emission control strategy, the major factors affecting the flue-gas emissions have been determined. A simulator has been constructed, and it emulates a real process automation system and its physical processes. The process models of the simulator are: a flue-gas oxygen-content model, a secondary air flow model, a primary air flow model and a fuel feeding screw model (a fuel flow). The effort has been focused on two plant models: the flue-gas oxygen-content model and the secondary air flow model. Combustion is a non-linear, timevariant, multi-variable process with a variable delay. The secondary air model is a non-linear, timeinvariant (in principle), multi-variable system. Both phenomenological modelling (mass and energy calculations) and black-box modelling (neural networks) have been utilised in the Wiener/Hammerstein structures. It is possible to use a priori knowledge in model modifying, and therefore the model of flue-gas oxygen-content can be tuned on site. The simulator with precalculated parameters was tested in a full-scale power plant and a pilot-scale circulating fluidised bed boiler. The results in the power plant were remarkable since NOx emissions decreased significantly without increasing CO emissions.

Carbon dioxide CO₂capture through hydrate formation is a novel technology under consideration as an efficient means of separating CO₂from flue/fuel gas mixtures for sequestration and enhanced oil recovery operations. This thesis examines post-combustion capture of CO₂from fossil-fuel power plant flue-gas streams through hydrate formation in a silica gel column. Power plant flue-gas contains essentially CO₂and nitrogen (N2) after suitable pre-treatment steps, thus a model flue-gas comprising 17% co₂and 83% N2 was used in the study. Previous studies employed a stirred-tank reactor to achieve water-gas contact for formation of hydrates; recent microscopic studies involved using water dispersed in silica gel to react with gas, showing potential for improved hydrate formation rates without the need for agitation. This study focuses on macroscopic kinetics of hydrate formation in silica gel to evaluate hydrate formation rates, CO₂separation efficiency and determining optimal silica gel properties as a basis for a CO2 capture process. Spherical silica gels with 30.0 and 100.0 nm pore sizes and 40-75 and 75-200 μm particle sizes were studied to determine pore size and particle size effects on hydrate formation. 100.0 nm pores achieved higher gas uptake and CO₂recovery over the 30.0 nm case. Improved CO₂separation was obtained when 75-200 μm particles with 100.0 nm pores were used. The two effects observed are due to improved gas diffusion occurring with larger pore and particle size, favouring increased hydrate formation. Compared to stirred-tank experiments, results in this study show a near four-fold increase in moles of gas incorporated in the hydrate per mole of water, showing that improved water-to-hydrate conversion is obtained with pore-dispersed water. At similar experimental conditions, CO₂recovery improved from 42% for stirred-tank studies to 51% for the optimum silica (100.0 nm 75-200 μm) determined in this study. Finally, effects of tetrahydrofuran (THF) - an additive that reduces operating pressure were evaluated. Experiments with 1 mol% THF, the optimum determined from previous stirred tank studies, showed improved gas consumption in silica but reduced CO₂recovery, indicating that the optimum concentration for use in silica is different from that in stirred-tank experiments. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Thesis is focused on calculation of the condenser of flue gas, which is created by burning of natural gas. In the first part is theoretical overview of equations describing film condensation and physical properties of the flue gas. The second part deals with practical thermal calculation of the specified condenser. In third part parametric study is done in which a tempature of cooling water at inlet and the coefficient of excess air are changed. The last part of the thesis is dedicated to geometric design of the flue gas condenser whose required power is 8 MW.

This master`s thesis is focused on possibility of use of flue gas as source of CO2 for algae cultivation in bioreactors. The first part of the master`s thesis is devoted to a qualitative and quantitative description of flue gas sources as CO2 source for algae cultivation. In the thesis industry sectors with the largest share of CO2 emissions on a global scale and in the Czech republic are summarized. On the basis of these data it was possible to determine cheap sources of CO2 for algae cultivation producing valuable biomass and other bio-products. The composition of flue gas from these sources was discussed in this section also with given expected outlook within the following years. The next part of the thesis is devoted to the influence of flue gas properties on algae cultivation. The impact of flue gas individual parameters on cell growth rate, quality and composition of biomass is described there. The description and design of the bioreactor is processed in the next part of the thesis. The experimental part of the thesis was performed on a bioreactor with similar properties. The next part of the thesis describes the effect of light on algae cultivation and the design of a regulation scheme for bioreactor light source. The experimental part of the thesis describes methods used to determine the concentrations of flue gas substances that could pass from flue gas into cultivation medium for algae cultivation to measure the changing composition of the flue gas in the closed experimental bioreactor system. The processed data from experimental measurements are presented and are discussed. The change in the composition of the culture medium for algae (without the presence of algae) due to flue gas aeration was monitored in the experimental part. It includes also the measurement of the change in the composition of the flue gas in time. All obtained and collected information are then summarized and discussed in the final part of the master`s thesis.

Performance testing methods of boilers in transient operating conditions (start, stop and combustion power modulation sequences) need the combustion rate quantified to allow for the emissions to be quantified. One way of quantifying the combustion rate of a boiler during transient operating conditions is by measuring the flue gas flow rate. The flow conditions in chimneys of single family house boilers pose a challenge however, mainly because of the low flow velocity. The main objectives of the work were to characterize the flow conditions in residential chimneys, to evaluate the use of the Pitot-static method and the averaging Pitot method, and to develop and test a calibration method for averaging Pitot probes for low 𝑅𝑅𝑅𝑅.A literature survey and a theoretical study were performed to characterize the flow conditions in in single family house boiler chimneys. The flow velocities under normal boiler operating conditions are often below the requirements for the assumptions of non-viscous fluid justifying the use of the quadratic Bernoulli equation. A non-linear calibration coefficient is required to correct for these viscous effects in order to avoid significant measurement errors. The flow type in the studied conditions changes from laminar, across the transition regime, to fully turbulent flow, resulting in significant changes of the velocity profile during transient boiler operation. Due to geometrical settings occurring in practice measurements are often done in the hydrodynamic entrance region, where the velocity profiles are neither fully developed nor symmetrical. The predicted changes in velocity profiles are also confirmed experimentally in two chimneys.Several requirements set in ISO 10780 and ISO 3966 for Pitot-static probes are either met questionably or not met at all, meaning that the methods cannot be used as such. The main issues are the low flow velocity, viscous effects, and velocity profiles that change significantly during normal boiler operation. The Pitot-static probe can be calibrated for low 𝑅𝑅𝑅𝑅, but is not reliable because of the changing velocity profiles.The pressure averaging probe is a simple remedy to overcome the problems with asymmetric and changing velocity profiles, but still keeping low the irrecoverable pressure drop caused by the probe. However, commercial averaging probes are not calibrated for the characterized chimney conditions and the information available on the performance of averaging probes at low 𝑅𝑅𝑅𝑅 is scarce. A literature survey and a theoretical study were done to develop a method for calibrating pressure averaging probes for low 𝑅𝑅𝑒 flue gas flows in residential chimneys.The experimental part consists of constructing a calibration rig, testing the performance of differential pressure transducers, and testing a prototype pressure averaging probe. The results show good correlation over a wide operation range, but the low 𝑅𝑅𝑅𝑅 characteristics of the probe could not be identified due to instability in the chosen pressure transducer, and temperature correlation for one of the probes while not for the other. The differential pressures produced are close to the performance limitations of readily available transducers and it should be possible to improve the method by focusing on finding or building a suitable pressure transducer. The performance of the averaging method can be improved further by optimizing the geometry of the probe. Another way of reducing the uncertainty would be to increase the probe size relative to the conduit diameter to produce a higher differential pressure, at the expense of increasing the irrecoverable pressure drop.

The Diploma’s work deals with design to use new methods of cleaning the combustion products for the incinerator of biomass, which guarantees removal of dioxins from the combustion products. Thesis depicts methods of cleaning the combustion products, like ADIOX, using ceramic filters, catalytically filters and methods REMEDIA. Thesis compares constituent methods in terms of effectiveness and according to economic analysis applicable to incinerator of biomass-power output 1 MW. Thesis acquaints with the conception of biomass and with thermic processing, which produces dioxins. Thesis processes using biomass in Czech Republic and plan for using in the future. Thesis processes detailed model of filter using the fabric filters REMEDIA. Suggestion of position of the filter and it is connection to original products line of cleaning the combustion products. Increased pressure loss of the new pipework way and increased consumption of ventilator incinerator is calculated for the new connection. In quest of decreasing the thermal loss of combustion products and in quest of increasing safety of operation is calculated and in quest of increasing safety of operation is calculated proposal of isolation for the filter and pipework. In the end of the thesis is depicted using the technology for decreased amount of dioxins from the fly ash from dioxin filter.

More than a hundred years ago, the world was affected by the infamous pandemic virus, the Spanish flu, which lasted from 1918 to 1920. During this period, the First World War broke out. In the spring of 2020, the world was affected by a new pandemic virus called the Coronavirus (COVID-19). For the people who lived during 1918–1920 and the present, each virus has had enormous repercussions on their own lives and safety. For each epidemic, it has meant the political and economic stability in the world has been exposed. The world from then and now differs immensely from each other. Today, there are alternative opportunities to replace the regular lessons with digital connection. This study will make a historical comparative study between the Spanish flu and the coronavirus. In this study, two magazines aimed at teachers will be selected for each pandemic. This is done to see how the schools were affected by each epidemic, what measures were taken against the infection and what difficulties arose with it.

Algae are microscopic organisms with a great potential to produce biomass and lipids at productivities several times higher than terrestrial crops. To grow, these organisms consume carbon dioxide (CO2), a greenhouse gas. This gas, emitted primarily by power plants after coal burning, can be effectively used for algae production, thus resulting in CO2 remediation and biomass beneficial utilization as feedstuff, industrial filler and biodiesel feedstock. However, since coal is a fuel mined from the earth’s crust, it contains heavy metals that are released during coal burning and inevitably enter the algal cultivation system, contaminating the water were algae is grown, the algal biomass and the products derived from such biomass. The distribution of heavy metals from flue gas in algal cultivation systems is unknown, yet necessary to advance this industry. This study focused on quantifying the distribution and effects that ten coal-derived heavy metals (Cu, Co, Zn, Pb, As, Se, Cr, Hg, Ni and Cd) will have on algae strain Scenedesmus obliquus and on the potential products derived from this algae.

A research report submitted in partial fulfilment requiremenrs of degree Master of Science tothe School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, South Africa, January 2018 / South Africa’s energy sector is vital to the development of its economy. Instability in the form of disruption in supply affects production costs, investments, and social and economic growth. Domestic sources are no longer able to meet the country’s demands. South Africa must find a local alternative fuel source in order to reclaim stability and encourage social and economic development. Biomass is one of the most abundant renewable energy sources, and has great potential as a fuel source. Currently biomass contributes 12% of the world’s energy supply, while in some developing countries it is responsible for up to 50% of the energy supply. South Africa is the highest maize producer on the African continent. Many studies carried out indicated that maize, and its residue contain valuable materials, and has the highest lower heating value in comparison to other agricultural crops. This indicates that maize can be a potential biomass for renewable energy generation in South Africa. A means for energy conversion for biomass, is the process of gasification. Gasification results in gaseous products H2, CO and CO2. Since the process of biomass gasification involves a series of complex chemical reactions involving a number of parameters, which include flow, heat transfer and mass transfer, it is very difficult to study the process of gasification by relying on experimentation only. Numerical simulation was used to provide further insight on this process, and accelerate development and application of maize gasification in a cost effective and efficient manner. The objective of this study was therefore, to verify and evaluate the feasibility of maize gasification and liquid fuels production in South Africa from an economic and energy perspective. The simulation model was developed in Aspen Plus® based on two thermodynamic models specified as Soave – Redlich – Kwong and the Peng Robinson equation of state. All binary parameters required for this simulation were available in Aspen Plus®. The gasification unit was modelled based on a modified Gibbs free energy minimization model. Gasification of maize and downstream processing in the form of Fischer-Tropsch (FT) synthesis and gas to liquids (GTL) processing for liquid fuels production was modelled in Aspen Plus®. Sensitivity analyses were carried out on the process variables: equivalence ratio (ER), steam to biomass ratio (SBR), temperature and pressure, to obtain the optimum gasification conditions. The optimum reactor conditions, which maximized syngas volume and quality was found to be an ER of 0.22 and SBR of 0.2 at a temperature of 611ºC. An increase in pressure was found to have a negative effect; therefore atmospheric conditions of 101.325 kPa were chosen, in order to maximize CO and H2 molar volumes. Based on these conditions the produced syngas consisted of 35% H2, 16% CO, 24% CO2 and 3%CH4. The results obtained from gasification, based on a modified Gibbs free energy model, show a closer agreement with experimental data, than other simulations based on the assumption that equilibrium is reached and no tar is formed. However, these results were still idealistic as it under predicted the formation of CO and CH4. Although tar was accounted for as 5.5% of the total product from the gasifier (Barman et al., 2012), it may have been an insufficient estimation resulting in the discrepancy in CO and CH4. The feasibility of maize as a feed for gasification was examined based on quality of syngas produced in relation to the requirements for FT synthesis. A H2/CO ratio of 2.20 was found, which is within range of 2.1 – 2.56 found to support greater conversions of CO with deactivation of the FT catalyst (Lillebo et al., 2017). The syngas produced from maize was found to have a higher H2/CO ratio than conventional fossil fuel feeds; implying that maize can result in a syngas feed which is both renewable and richer in CO and H2 molar volumes. Liquid fuels generation was modelled based on experimental production distributions obtained from literature for FT synthesis and hydrocracking. The liquid fuel production for 1000 kg/hr maize feed, was found to be 152 kg/hr LPG, 517 kg/hr petrol and 155 kg/hr diesel. The simulation of liquid fuels production via the Fischer-Tropsch synthesis and hydrocracking process showed fair agreement with literature. Where significant deviations were found, they could be reasonably explained and supported. This simulation was found to be a suitable means to predict liquid fuels production from maize gasification and downstream processing. The feasibility of liquid fuels production from maize in South Africa was examined based on the country’s resource capacity to support additional maize generation. It was found that based on 450 000 hectares of underutilized land found in the Homelands, an additional 1.216 billion litre/annum of synthetic fuels in the form of diesel and petrol could be produced. This has the potential to supplement South African liquid fuels demand by 6% using a renewable fuel source. This fuel generation from maize will not impact food security due to the use of underutilized arable land for maize cultivation, or impact water supply as maize does not require irrigation. In addition, fuel generation in this manner supports the Biofuels Industry Strategy (2007) by targeting the use of underutilized land, ensuring minimal impact on food security, and exceeds its primary objective of achieving a 2% blending rate from renewable sources. The economic feasibility of liquid fuels derived from maize was determined based on current economic conditions in 2016. Based on these conditions of 49 $/bbl Brent Crude, 40 $/MT coal and 6.5 $/mmBTU of natural gas at a R/$ exchange rate of R14.06 per U.S. dollar, it was found that coal, natural gas and oil processing are more economically viable feeds for fuel generation relative to maize. However, based on projected market conditions for South Africa, the R/$ exchange rate is expected to weaken further, the coal supply is expected to diminish and supply of natural gas is expected to be a continued issue for South Africa. Based on this, maize should be considered as a feed for fuel generation to reduce the dependency on non-renewable fossil fuel sources. The energy feasibility of liquid fuels produced from maize was only evaluated from a thermal energy perspective. It was found that maize gasification and FT processing requires 0.91 kg steam/kg feed. This 0.91kg of steam accounts for the raw material feed, distillation and heating required for every 1kg of maize processed. It was found that 2.56 kg steam/kg feed was generated from the reactor units. This was assumed to be in the form of 10 bar steam, as in this form it can be sent to steam turbines for electricity generation to assist with overall energy efficiency for this process. In addition, the amount of CO2 (kg/kg feed) produced, was examined for maize processing in comparison to fossil fuel feeds: natural gas and coal. The CO2 production from liquid fuels processing based on a maize feed, was found to be the highest at 0.66 kg/kg feed. However, a coal feed has higher ash and fix carbon content indicating greater solid waste generation in the gasifer. While dry reforming of natural gas is a net consumer of CO2, but had significantly higher steam requirements in order to achieve the same H2/CO ratio as maize. This indicates that although maize results in more CO2/kg feed, it is 88% more energy efficient than dry methane reforming. Additional experimental work on FT processing using syngas derived from maize is recommended. This will assist in further verification of liquid fuels quantity, quality and process energy requirements. / XL2018