Effective control of nitrification processes employed at municipal wastewater treatment plants is essential for maintaining process reliability and minimizing environmental impacts and operating costs. While a range of process control strategies are available, they share a dependence on invasive liquid phase monitoring and are based on a periphery understanding of the metabolic status of the processes being controlled. Utilization of off-gas nitrous oxide (N2O) monitoring as a real-time indicator of the process metabolic status is a novel process control concept with the potential to address these concerns. This thesis details the development and evaluation of an off-gas N2O stress response based control technique. Examination of the stress response relationship demonstrated that it met the majority of the criteria of interest for process control. A simple feedback aeration control strategy was developed and evaluated through process simulation to determine the feasibility of implementation, cost effectiveness and associated environmental benefits. The off-gas N2O based control strategy provided better matching between aeration supply and metabolic demand, allowing the process to be maintained at the desired operating setpoints and avert nitrification failure. Performance was demonstrated to be similar to dissolved oxygen based feedback aeration control, although slightly more efficient at reduced dissolved oxygen concentrations. A technical, economic and environmental evaluation indicated that aeration control based on non-invasive off-gas N2O monitoring is technically feasible and has the potential to offer significant environmental and economic benefits including reductions in operating costs and process capital investment, as well as improved effluent compliance and reductions in emissions of gaseous pollutants including greenhouse gases. Overall, while off-gas N2O monitoring based aeration control techniques have the potential to provide significant economic and environmental benefits, a number of research questions remain to be answered. Future work in the form of long-term field trials is required to address these issues and allow quantification of economic and environmental benefits.

Effective control of nitrification processes employed at municipal wastewater treatment plants is essential for maintaining process reliability and minimizing environmental impacts and operating costs. While a range of process control strategies are available, they share a dependence on invasive liquid phase monitoring and are based on a periphery understanding of the metabolic status of the processes being controlled. Utilization of off-gas nitrous oxide (N2O) monitoring as a real-time indicator of the process metabolic status is a novel process control concept with the potential to address these concerns. This thesis details the development and evaluation of an off-gas N2O stress response based control technique. Examination of the stress response relationship demonstrated that it met the majority of the criteria of interest for process control. A simple feedback aeration control strategy was developed and evaluated through process simulation to determine the feasibility of implementation, cost effectiveness and associated environmental benefits. The off-gas N2O based control strategy provided better matching between aeration supply and metabolic demand, allowing the process to be maintained at the desired operating setpoints and avert nitrification failure. Performance was demonstrated to be similar to dissolved oxygen based feedback aeration control, although slightly more efficient at reduced dissolved oxygen concentrations. A technical, economic and environmental evaluation indicated that aeration control based on non-invasive off-gas N2O monitoring is technically feasible and has the potential to offer significant environmental and economic benefits including reductions in operating costs and process capital investment, as well as improved effluent compliance and reductions in emissions of gaseous pollutants including greenhouse gases. Overall, while off-gas N2O monitoring based aeration control techniques have the potential to provide significant economic and environmental benefits, a number of research questions remain to be answered. Future work in the form of long-term field trials is required to address these issues and allow quantification of economic and environmental benefits.

The thesis is focused on analyzing the current status of the technology used for cleaning flue gas from persistent organic pollutants, especially PCDD/F. For the three most commonly used methods of solution operational and energy efficiency comparison was made, where achievable energy export and the impact of the change in working conditions on the efficiency indicators of energy production and use of the energy was evaluated. In conditions we considered an alternative machine-technological solutions used for the final disposal of persistent organic pollutants resulting from the waste combustion in terms of additional operating costs and energy efficiency.

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: In a minerals processing environment, stable production processes, cost minimisation and energy efficiency are key to operational excellence, safety and profitability. At an ilmenite smelter, typically found in the heavy minerals industry, it is no different. Management of an ilmenite smelting process is a complex, multi-variable challenge with high costs and safety risks at stake. A by-product of ilmenite smelting is superheated carbon monoxide (CO) gas, or furnace off-gas. This gas is inflammable and extremely poisonous to humans. At the same time the gas is a potential energy source for various on-site heating applications. Re-using furnace off-gas can increase the energy efficiency of the energy intensive smelting process and can save on the cost of procuring other gas for heating purposes. In this research project, the management of CO gas from the Tronox KZN Sands ilmenite smelter in South Africa was studied with the aim of optimising the current utilisation of the gas. In the absence of any buffer capacity in the form of a pressure vessel, the stability of the available CO gas is directly dependent on the stability of the furnaces. The CO gas has been identified as a partial replacement for methane gas which is currently purchased for drying and heating of feed material and pre-heating of certain smelter equipment. With no buffer capacity between the furnaces and the gas consuming plants, a dynamic prioritisation approach had to be found if the CO was to replace the methane. The dynamics of this supply-demand problem, which has been termed the “CO gas problem”, needed to be studied. A discrete-event simulation model was developed to match the variable supply of CO gas to the variable demand for gas over time – the demand being a function of the availability of the plants requesting the gas, and the feed rates and types of feed material processed at those plants. The problem was formulated as a multi-objective optimisation problem with the two main, conflicting objectives, identified as: 1) the average production time lost per plant per day due to CO-methane switchovers; and 2) the average monthly saving on methane gas costs due to lower consumption thereof. A metaheuristic, namely multi-objective optimisation using the cross-entropy method, or MOO CEM, was applied as optimisation algorithm to solve the CO gas problem. The performance of the MOO CEM algorithm was compared with that of a recognised benchmark algorithm for multi-objective optimisation, the NSGA II, when both were applied to the CO gas problem. The background of multi-objective optimisation, metaheuristics and the usage of furnace off-gas, particularly CO gas, were investigated in the literature review. The simulation model was then developed and the optimisation algorithm applied. The research aimed to comment on the merit of the MOO CEM algorithm for solving the dynamic, stochastic CO gas problem and on the algorithm’s performance compared to the benchmark algorithm. The results served as a basis for recommendations to Tronox KZN Sands in order to implement a project to optimise usage and management of the CO gas. / AFRIKAANSE OPSOMMING: In mineraalprosessering is stabiele produksieprosesse, kostebeperking en energie-effektiwiteit sleuteldrywers tot bedryfsprestasie, veiligheid en wins. ‘n Ilmenietsmelter, tipies aangetref in swaarmineraleprosessering, is geen uitsondering nie. Die bestuur van ‘n ilmenietsmelter is ‘n komplekse, multi-doelwit uitdaging waar hoë kostes en veiligheidsrisiko’s ter sprake is. ‘n Neweproduk van die ilmenietsmeltproses is superverhitte koolstofmonoksiedgas (CO gas). Hierdie gas is ontvlambaar en uiters giftig vir die mens. Terselfdertyd kan hierdie gas benut word as energiebron vir allerlei verhittingstoepassings. Die herbenutting van CO gas vanaf die smelter kan die energie-effektiwiteit van die energie-intensiewe smeltproses verhoog en kan verder kostes bespaar op die aankoop van ‘n ander gas vir verhittingsdoeleindes. In hierdie navorsingsprojek is die bestuur van die CO gasstroom wat deur die ilmenietsmelter van Tronox KZN Sands in Suid-Afrika geproduseer word, ondersoek met die doel om die huidige benuttingsvlak daarvan te verbeter. Weens die afwesigheid van enige bufferkapasiteit in die vorm van ‘n drukbestande tenk, is die stabiliteit van CO gas beskikbaar vir hergebruik direk afhanklik van die stabiliteit van die twee hoogoonde wat die gas produseer. Die CO gas kan gedeeltelik metaangas, wat tans aangekoop word vir die droog en verhitting van voermateriaal en vir die voorverhitting van sekere smeltertoerusting, vervang. Met geen bufferkapasiteit tussen die hoogoonde en die aanlegte waar die gas verbruik word nie, was die ondersoek van ‘n dinamiese prioritiseringsbenadering nodig om te kon vasstel of die CO die metaangas kon vervang. Die dinamika van hierdie vraag-aanbod probleem, getiteld die “CO gasprobleem”, moes bestudeer word. ‘n Diskrete-element simulasiemodel is ontwikkel as probleemoplossingshulpmiddel om die vraag-aanbodproses te modelleer en die prioritiseringsbenadering te ondersoek. Die doel van die model was om oor tyd die veranderlike hoeveelhede van geproduseerde CO teenoor die veranderlike gasaanvraag te vergelyk. Die vlak van gasaanvraag is afhanklik van die beskikbaarheidsvlak van die aanlegte waar die gas verbruik word, sowel as die voertempo’s en tipes voermateriaal in laasgenoemde aanlegte. Die probleem is geformuleer as ‘n multi-doelwit optimeringsprobleem met twee hoof, teenstrydige doelwitte: 1) die gemiddelde verlies aan produksietyd per aanleg per dag weens oorgeskakelings tussen CO en metaangas; 2) die gemiddelde maandelikse besparing op metaangaskoste weens laer verbruik van dié gas. ‘n Metaheuristiek, genaamd MOO CEM (multi-objective optimisation using the cross-entropy method), is ingespan as optimeringsalgoritme om die CO gasprobleem op te los. Die prestasie van die MOO CEM algoritme is vergelyk met dié van ‘n algemeen aanvaarde riglynalgoritme, die NSGA II, met beide toepas op die CO gasprobleem. The agtergrond van multi-doelwit optimering, metaheuristieke en die benutting van hoogoond af-gas, spesifiek CO gas, is ondersoek in die literatuurstudie. Die simulasiemodel is daarna ontwikkel en die optimeringsalgoritme is toegepas.

Ingeniero Civil Químico / Ingeniero Civil en Biotecnología / La cobertura de tratamiento de aguas servidas en Chile alcanza al 83% del sistema sanitario. El proceso más habitual es lodos activos, que requiere transferir oxígeno a la velocidad adecuada para satisfacer la respiración de las bacterias que oxidan la carga orgánica del reactor, expresada precisamente como demanda de oxígeno. El oxígeno se suele suministrar como aire, mediante impulsión mecánica (sopladores o compresores), la que consume energía que resultaría optimizada en su costo si la eficiencia de transferencia de oxígeno fuese máxima. En esta memoria se construyó y operó un equipo normado para la determinación de la eficiencia de transferencia de oxígeno (OTE), en los reactores de lodos activos de una planta de tratamiento de aguas servidas de gran escala, bajo distintas condiciones de operación, reflejadas, por ejemplo, por diferentes calidades de agua y antigüedad de los difusores. El sistema utiliza el método de balance del gas de entrada y de salida (off-gas), que utiliza una cúpula flotante en el reactor biológico, para medir la fracción molar de oxígeno en el gas de salida y compararla con la de entrada (aire alimentado al reactor). Entre los indicadores de transferencia de oxígeno obtenidos, se calculó la eficiencia estándar de transferencia de oxígeno (SOTE) en condiciones de proceso. Casi en todos los casos, la SOTE en condiciones de proceso disminuyó entre 27 y 5% desde las 9 a las 20 horas, debido al sostenido aumento del flujo de aire por difusor necesario a lo largo de la jornada, entre 4 y 38 [Nm3/h] para el mismo rango horario. La comparación de los reactores con diferentes características del agua de proceso, mostró que la SOTE es mayor cuando el nivel de contaminación del agua es menor. Esto se observó mediante el factor alfa, número entre 0 y 1 que mide el grado de pureza del agua de proceso en comparación con el agua pura. En el caso de uno de los reactores, que recibe agua con un grado más avanzado de tratamiento, se obtuvieron SOTEs entre 28 y 12% para mediciones entre las 9 y 19 horas, mientras que para el otro reactor, que se encuentra antes en la serie de tratamiento (agua con menor factor alfa), las SOTEs obtenidas se movieron entre 20 y 7 %, en similar rango horario. No fue posible llegar a establecer reglas de optimización del proceso, pues el número de mediciones fue insuficiente para tal propósito. Se sugiere que el desarrollo requiere una observación experimental más prolongada, en reactores con diferentes características y, además, más rigurosas, destacándose la necesidad de disminuir la incertidumbre de las mediciones de temperatura, flujo y presión.

The main purpose of this thesis was to compare GAC adsorption method, VOCs incinerationmethod and Non-treatment alternative by using LCA to find which method or alternative isenvironmentally preferable. The LCA framework proposed by ISO 14040 (1997) has beenconsidered in this research. The comparison was made by considering a flue gas contaminatedby toluene (with three different concentration 100, 1000, 2000 mg/m3). The plant locationwhere the polluted flue gas is emitted has been assumed to be located in Borås, Sweden. Theflow rate of emitted flue gas was 10000m3/hr. The present thesis report contains two mainparts.The results of LCA showed that when the toluene concentration is low (< 100 mg/m3), GACadsorption method, Non-treatment alternative and VOCs incineration method are respectivelypreferable from environmental point of view. On the other side, when the tolueneconcentration of inlet stream is high (>1000 mg/m3), the order of GAC adsorption method,incineration and Non-treatment alternative is more desirable. Furthermore, the resultsillustrated that as toluene plays the role of fuel as a hydrocarbon, VOCs incineration methodis much more suitable when toluene concentration is high due to lower demand on additionalfuel. In the other words, high toluene concentration of influent leads to less environmentalimpact when VOCs incineration method is exploited. Conversely, the environmental impactof GAC adsorption method is increased when the inlet concentration of toluene is escalated.In overall, the weighted result showed that GAC adsorption method is the most preferablemethod while Non-treatment alternative is the worst.

A low-emissions power generator comprising a solid oxide fuel cell coupled to a gas turbine has been developed by Rolls-Royce Fuel Cell Systems. As part of the cycle, a fraction of the unreacted fuel (the off-gas) and oxidizer streams is reacted in a burner, which is the main source of pollutant formation. In this thesis a computational model of the burner has been developed which captures the formation of NOx and the oxidation of CO. This model gives accurate predictions at low computational cost, making it suitable for use as a design tool in future burner design optimization through parametric studies. A key factor in increasing computational efficiency was the development of a reduced H2/CO/N2 kinetic mechanism; from a starting mechanism of 30 species to 10 and 116 reactions to 6. The results of laminar opposed-flow diffusion flames have been used to validate the reduced mechanism. Several different turbulent combustion models have been evaluated by creating an interface between the reduced kinetic mechanism and the commercial CFD solver FLUENT. Comparison of model predictions with well-characterized turbulent syngas flames, which share a similar fuel composition to the experimental work conducted on the off-gas burner, shows acceptable agreement. These studies have demonstrated the sensitivity of modelling constants. Improved predictions were achieved by calibrating these constants and including radiative heat losses. Following suitable modification to reflect the predominantly laminar flow present in the current burner design, the relevant modelling approaches were applied to the off-gas burner. Comparison was made to previous detailed measurements, showing that the important trends of NOx and CO are captured in general. The model was extended to high pressure conditions, similar to those in the actual off-gas burner, with the emissions predictions within design limits. The outcome of this work is a fast, accurate design tool for CFD which has capabilities to simulate beyond the laminar burner studied here. It may be applied to more general types of off-gas/syngas burners where turbulence-chemistry interaction is expected to be more significant.

The main purpose of the AOD-converter is to lower the carbon content in stainless steel production. The carbon content can be estimated by static theoretical models. It can also be estimated through dynamic models based on analysis of the exhaust gases from the converter. This master thesis is a study on an extended use of exhaust gas analysis data on the AOD-converter at Outokumpu’s stainless steel plant in Avesta, Sweden. There are two main methods of predicting the carbon content based on exhaust gas analysis, mass balance and a linear regression between decarburization rate and carbon content. This master thesis mainly focuses on the development of the linear regression model for steel grades ASTM 304L, 316L, S32101 and S32205 for the last step of the decarburization, as well as ASTM S32205 and S30815 for the second last step of the decarburization. The results showed that the linear regression model can predict the carbon content at the last step of decarburization with a standard deviation between 0,00626 %C and 0,0109 %C for the different steel grades. An equation for carbon prediction dependent on the steel composition was also developed in the master thesis, making it theoretically possible to use for all steel grades, it has however not yet been tested on other steel grades. The CRE measured from the exhaust gases was also studied to find out if it is possibleto use as basis for step changes during the decarburization, but the resultswere inconclusive. / Huvudsyftet med AOD-konvertern är att sänka kolhalten i produktionen av rostfritt stål. Kolhalten kan uppskattas av statiska teoretiska modeller. Den kan också uppskattas av dynamiska modeller baserade på analys av avgaserna från konvertern. Det här examensarbetet handlar om utvidgning av användandet av avgasanalysdata på AOD-konvertern på Outokumpus stålverk i Avesta, Sverige. Det finns i huvudsak två metoder för att bestämma kolhalten med hjälp av avgasanalys, massbalans och en linjär regression mellan kolfärskningshastigheten och kolhalten. Det här examensarbetet fokuserar i huvudsak på utvecklingen av den linjära modellen för stålsorterna ASTM 304L, 316L, S32101 och S32205 för sista steget i kolfärskningen. Samt stålsorterna ASTM S32205 och S30815 för näst sista steget i kolfärskningen. Resultaten visade att den linjära modellen kunde uppskatta kolhalten i sista steget av kolfärskningen med en standardavvikelse mellan 0,00626 %C och 0,0109 %C för de fyra olika stålsorterna. En ekvation som anger sambandet mellan sammansättningen på stålet under kolfärskningen och ekvationen för den linjära regressionen togs också fram i examensarbetet. Teoretiskt kan ekvationen användas för alla stålsorter men den har inte än blivit testad på andra stålsorter. CRE uppmätt med hjälp av avgasanalys undersöktes också för att ta reda på om CRE kan användas för att bestämma när stegbytena ska ske, det gick dock inte att utgöra från resultaten.

Without a doubt, there is a consensus around the international community which suggests that our current way of life is unsustainable for a healthy planet, society and economy. One focal point that should be taken deeply into consideration is the steel industry as, globally, it accounts for 8% of global emissions. Thus, there is a dire need to incorporate drastic measures, if one wishes to reach net-zero emissions by 2050, in accordance with the Paris Agreement of 2015. Electric Arc Furnaces are seeing a rapid implementation in the steel industry. However, at 0.5 tonnes of CO2 emitted per tonne of liquid steel produced, this emissions rating is still significant considering the amount of steel being produced annually. Additionally, these furnaces emit off-gases which must be treated from the dust. This leaves operators with a conundrum as the dust content compromises the use of waste heat recovery boilers for energy recovery, due to constant breakdowns. Therefore, this study aims to analyse the feasibility of using bioenergy and carbon capture and utilisation (CCU) concepts to capitalise on the high off-gas energy and emissions content to remedy the dust issue, whilst producing higher value products. The proposed concept evaluates the effectiveness of using the off-gas as the energy carrier and feed-stock for a biogasificaiton unit. Three different cases based on different EAF off-gas compositions have been investigated. Case 1 suggested that the off-gas composition is very CO2-heavy, whichled to investigating the option of adopting a CO2 biogasification concept to directly use the CO2. Case 1 performed the best in terms of CO2 utilisation efficiency; being 0.293. The system energy utilisation also noted that 49.3% of the inlet streams energy was transferred to the desired product. On a broader picture, this means that around 11% of the total energy coming out of the EAF would be utilised in producing a value-added product in the form of syngas. This contrasts with allowing around 33% of the energy in the EAF either being completely dissipated to the environment or converting it into electricity via waste heat recovery. The following two cases, Case 2 and 3, indicate EAF off-gas composition containing 72% and 40% nitrogen respectively. For Cases 2 and 3, a steam biogasification process was integrated which did not yield positive results for CO2 utilisation, since is a more promising gasifying agent. In addition, significant energy from EAF off-gas is used in raising the temperature of steam to the design temperature of the gasifier. However, although the CO2 was not directly used in this part of the process, it allows for other opportunities of process integration, for example the reverse water-gas shift step.

A detailed study has been carried out to demonstrate the importance of external and internal mass transfer on the nitrification rates in three distinct treatment processes: flocculent and granular activated sludge, and suspended carrier reactor (SCR) systems. The major emphasis was on external mass transfer, and the impact of system hydrodynamics on this mechanism. Laboratory-scale flocculent and granular sequencing batch reactors were operated for the nitrification of a synthetic wastewater. A two-stage, continuous, nitrifying SCR was operated using the same wastewater feed. Within each stage, biofilm was grown on two types of commercial carriers- the Natrix C10/10 from ANOX AB (Sweden); and the K1 carrier from Kaldnes Miljøteknologi (Norway). Biofilm carriers obtained from each of these reactors was utilised for the mass transfer investigations. The major findings, and contributions of the work to the field of biological wastewater treatment, are described in the following paragraphs. In order to complete the work, a novel experimental tool, the TOGA (Titrimetric and Off-Gas Analysis) sensor was created, which utilises off-gas mass balancing, coupled with pH titration to provide detailed measurement of biological reaction rates. An original method for off-gas mass balancing was developed, within a reactor that allowed modification of the hydrodynamic conditions using gas phase mixing independent of dissolved oxygen control within the liquid phase. This sensor has already proven to be a highly effective tool not only for the measurement of oxygen but also for carbon dioxide and various nitrogen species, and has application for numerous other compounds present in the gas phase of biological reactors (e.g. hydrogen, methane). The application of the TOGA sensor signals to the nitrification process was demonstrated, which enabled the online measurement of oxygen, ammonia, and nitrite reaction rates. The TOGA sensor development underpinned the majority of the subsequent experimental work within this thesis. Dissolved oxygen microelectrodes were also used, enabling microscale measurements to be made in conjunction with the macroscale TOGA sensor analyses. Combined with size and microbiological analyses a detailed study of mass transfer and reaction was able to be carried out on the various systems. For suspended aggregate systems (flocs and granules): A spherical particle model was developed and used to predict the potential for external mass transfer limitation in flocs and granules. The significance of this limitation was confirmed experimentally, by observing changes in reaction rate or concentration boundary layer (in the TOGA sensor or microelectrode study, respectively) upon modification of the system’s flow conditions. Despite this flow effect being small, and only observable under low bulk liquid substrate concentrations, the external mass transfer limitation was concluded to be significant for biological flocs and granules even at higher substrate concentrations. As particle size and the maximum volumetric reaction rate of the biomass increases, external mass transfer effects become increasingly significant. The work highlights the impact of mass transfer limitation on the measurement of Monod half saturation coefficients (KS) in flocs and granules. Without accounting for external or internal mass transfer limitation, KS is seriously overestimated and becomes a lumped parameter, reflecting not only the microbial response but also the mass transfer limitations observed within the system under study. To avoid confusion or generation of erroneous results, care should be taken in defining, measuring and utilising the half saturation coefficient in biological systems where the biomass is not present as individual cells or extremely small flocs. For Suspended Carrier Reactor systems: External and internal mass transfer are both concluded to be important rate limiting steps within suspended carrier reactors. The demonstration of a significant impact of fluid flow conditions on the nitrification rates highlights the impact of external mass transfer limitation within these systems. Application of a one-dimensional biofilm model to the experimental results led to the conclusion that there is little difference between the external mass transfer limitation of the two different carrier types, for carriers grown under the same environmental conditions. However, there was a significantly higher areal nitrification rate observed on the Natrix carriers compared to the Kaldnes carriers. It is the biofilm structure that is critically important in characterising the mass transfer steps. Systems operated under high nitrogen loads, producing filamentous biofilms on the carrier surface, were found to have larger external mass transfer coefficients and responses to changes in fluid flow than those carriers which were operated under nitrogen-limited conditions (producing a flatter, more gel-like biofilm). The structure of the biofilm colonising the carrier surface was far more important in defining the mass transfer coefficient than the actual carrier type used. In a remarkably similar trend to that of the external mass transfer coefficient, the biofilm morphology was again significantly more important than carrier type in determining both the magnitude and response to fluid flow of the gas-liquid mass transfer coefficient for oxygen (kLa) calculated within the laboratory TOGA sensor. These findings led to the postulation that direct gas-biofilm interfacial mass transfer mechanism is occurring within the SCR systems. This hypothesis is an alternative to the standard mechanism of gas transfer from the bubble into the liquid phase, and then into the biofilm. Understanding of interfacial transfer is likely to be important for developing the knowledge of SCR processes. Overall, both external and internal mass transfer phenomena have been demonstrated to create important rate limitations to suspended aggregate systems (flocs and granules) and biofilms grown in suspended carrier reactors. This significantly advances the conceptual understanding of these biological treatment processes.