published_or_final_version / Geography and Geology / Master / Master of Philosophy

<p>The primary aim of these coal fired industries for co-disposing fly ash and brine was to use the fly ash as a sustainable salt sink. It is therefore important to study the interaction chemistry of the fly ash-brine systems to fully understand the leaching and mobility of the contaminant species, and to determine the possibility of capturing the salts from the brine solution when fly ash and brine are co-disposed. In order to achieve the aims and objectives of this study, several leaching procedures such as batch reaction tests, long-term fly ash-brine interaction tests, acid neutralization capacity (ANC) tests, up-flow percolation tests and sequential extraction tests were employed. The geochemical modeling software was applied to predict the formation of secondary mineral phases controlling the release of species in the fly ash-brine systems. Several analytical techniques such as x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), inductively coupled plasma-mass spectroscopy (ICP-MS) and ion chromatography (IC) were applied to characterize the fresh fly ashes, solid residues recovered from the fly ash-brine interaction tests, the brine sample used in this study and the leachate samples in order to determine the chemical and mineralogical compositions and speciation of the waste materials.</p>

Two coal utility plants in South Africa selected (one from Sasol and another from Eskom) for this study produce large volumes of fly ash (over 40 Mt from Eskom at Tutuka, and 3 Mt from Sasol Synfuels at Secunda annually), and brines as by-products during coal processing. Co-disposal of the brines and fly ashes has been a normal practice in these coal-utility plants for decades. Long-term management of fly ash is necessary and requires an understanding and knowledge of how the different waste materials interact with water and brines in different chemical situations. However the geochemistry of their interactions, the leaching and mobility of elements in these disposal systems has not been fully understood. This work gives insights into the chemical processes taking place in the brine-water/brines systems that govern the concentrations of major and minor elements in ash leachates under different environmental conditions. The possible presence of organic compounds (subsequently referred to as 'organics') in brines and their effects on the leaching chemistry of fly ash was also studied. Sustainability and long term impact of the co-disposal of fly ash and brines on the environment was studied through static (batch tests) modeling of the pH-dependent acid neutralization capacity (ANC) tests and columns modeling for dynamic leach tests. The modeling was based on experimental results from other Sasol-Eskom ashbrine project collaborators. Modeling results of the ANC tests were in good agreement with the reported experimental results, which revealed that the release trends of various elements (including trace, heavy elements and contaminants) contained in fly ash into solution is highly pH dependent. However Na, K, Mo and Li exhibited constant solubilisation which was independent of pH changes from all the scenarios. The presence of different constituents of brines subjected to ANC resulted to different ANC capacities ranging from 0.98 moles H⁺/Kg dry ash (of ash-organics mixed with Mg-brines) to 3.87 H⁺/Kg dry ash for those with the C(4) brines. As expected, those constituents from the cationic brines were found on the lower region of acid addition (in the order Mg-brines < Ca-brines < Na-brines) while the anionic brines were found at the upper region of acid addition (in the order S(6)-brines < Cl-brines < C(4)-brines). In the middle region of acid addition were three important scenarios: that of ash with brine, ash without brines (i.e. ash with DMW) and ash with both ASW organics and combined brines. It was from these three scenarios that a generalization of the effect of brines and organics on the ANC was inferred. The ANC of ash with demineralised water (DMW) was 2.33 mol H⁺/Kg dry ash and that of ash with ASW organics lower at 2.12 mol H⁺/Kg dry ash which was the same value as that of ash with combined brines. This indicated that brines decreased the ANC of ash by about 9.01 % and which could be attributed to the acid-base neutralization process and the dynamics of solid phase dissolutions in response to the acid addition. Both fly ashes exhibited a typical pH > 12 (suspension in demineralised water) and the predominant cation even at this high pH is Ca²⁺ (at concentration > 0.002 mmol/L). This indicates that dissolution of CaO and formation of OH⁻ species at pH > 10 contributes to acid neutralisation capacity of both fly ashes and is the greatest contributor to the acid neutralizing capacity of both fly ashes. Two broad leaching behaviours as a function of pH were observed from the three fly ash-ASW organics-brines scenarios (i) leaching of Ca, Mg, Ni and Sr follows a cationic pattern where the concentration decreases monotonically as pH increases; (ii) leaching of Al, Fe, Ti and Zn follow an amphoteric pattern where the concentration increases at acidic and alkaline pH, although Al showed some anomaly from pH 11 where the concentration decreased with the increase in pH. Al showed an amphoteric pattern in which its release increased between pH 12.8 and 11 for all the scenarios and then decreased with decrease in pH down to neutral pH of 7. The batch leaching simulation results from hydrogeochemical modeling also showed that mineral dissolution, precipitation and new phase formation during ash-organics-brines interactions was controlled by pH. The newly formed phases however remain in equilibrium with the ash-brines-organics mixture. Each individual mineral phase dissolution/precipitation/formation system controls the concentration and speciation of the respective constituent elements as evidenced by the log C-pH diagrams obtained from the modeled scenarios. The ash-brines-organics interactions do exhibit and affect the mineralogical chemistry of fly ash. However the extent to which these interactions occur and their effect, varies from one scenario to another, and are dependent on the amounts and type of the constituent brine components. Organics do have a significant effect on dissolution characteristics of few minerals such as calcite, mullite, kaolinite, Ni₂SiO₄, and SrSiO₃ due to complexation effect. The effect is quantitatively conspicuous for calcite mineral phase and for the formation of some new phases such as Fe(OH)₃(am)-CF and portlandite. The composition of the liquid phase from acid neutralisation capacity experiments was successful.Hydrogeochemical modeling was used as a means to provide insights and understanding of the complex reactions taking place, speciation and mineralogical changes occurring. These changes would serve to predict future environmental scenarios when pH conditions change. In this study, an extension of the application field of PHREEQC hydrogeochemical code for modeling and simulation of equilibrium; kinetic and transport mechanisms associated with the interaction of water; and organics and brines with fly ash during their co-disposal is successfully demonstrated. The parameters associated with these mechanisms were used as inputs into the PHREEQC program using modified Lawrence Livermore National Laboratory (LLNL) database for inorganic brines and MINTEQ.V4 database for organics, and used to model the results of ANC test data for the fly ashes. A special reference is made to two separate modeled mineralogical ash recipes from two of the South African power utility plants' fly ash systems, namely, Tutuka and Secunda. The effects of brines in the leaching of major, minor and trace elements at various pH values and the mineralogical changes associated with the intermediate and final products from the interactions of ash-brines systems under different scenarios are qualitatively and quantatively discussed. Multiphase saturation characteristics have been determined for mineral species in contact with water and brines. The modeling results indicated that several mineral phases could be controlling the species concentration in the leachates, and the ANC and column modeling results corroborated well in many aspects with the experimental results obtained from collaborating institutions (South Africa Universities and Research institutions). In addition, application of the PHREEQC model to the ash heap under different disposal systems was carried out to predict the heap leachate composition and geochemical transformations taking place in a period of time. Pore water chemical analysis, and moisture content analysis revealed that contact of the ash with water is a crucial factor in the mobilization of the contaminants with time. Maximum weathering/dissolution of the ash is observed in the top layer (1-3) m and at the point of contact with the subsurface water level which was in good agreement with the model results. The surface layer and the very lowest layers of the dump in contact with lateral flows experience the highest degree of weathering leading to depletion of species. The geophysical transformation of fly ash was also captured through the porosity change calculations and the results revealed that geochemical reactions do affect the porosity of fly ash during the weathering processes. These modelling results were in agreement with the hydraulic tests and salt leaching tests conducted during Sasol-Eskom ashbrine project in Phase I which suggested that salts captured in the ash will become mobile and leach from the fly ash over time. The data therefore indicates that ash dumps may not act as sustainable salt sinks. These findings may have some bearing on engineering decisions on fly ash reuse. From the above observations, it is apparent that release of large quantities of the salts in the ash depends on the extent of its interaction with brines being used for irrigation or with water, either through plug-in flow after a rainfall event or contact with groundwater. The results revealed effects of brine-water contact time with fly ash, the flow volume and velocity, the pH, the degree of saturation, hydrogeology and ash heap geometry as important factors that affect fly ash transformation and weathering. Overall, the ash heap modeling enhanced the understanding of the ash-brines interactions and demonstrated that leachate composition is determined by the following factors; (i) the mass flows from the pores of fly ash, (ii) the surface dissolution of the mineral phases, (iii) the various chemical reactions involved during the ash-brine and ash-water interactions, (iv) the interactions with a gas phase (atmospheric CO₂), (v) the composition of the initial fly ash, and (vi) by the leachate flow and hydrodynamics as captured in the conceptual model. Any ash handling system should therefore be designed to take these criteria into consideration to prevent environmental contamination. The modeling results also gave indications that the ash-brine co-disposal in dry ash systems would be an unsustainable way of locking up brine salts in the long run. In this Thesis, modeling results were used to support experimental data which further reaffirmed the important role hydrogeochemical modeling plays in liquid and solid waste management. Furthermore, hydrogeochemical modeling complements the work of analytical/environmental scientists as well as guiding the future solid waste management and engineering decisions. / Thesis (Ph.D.)-University of KwaZulu-Natal, Westville, 2012.

In this investigation, SCCs were prepared by keeping the total mass of cementitious materials (cement and fly ash) constant at 500 kg/m3, in which 30, 40, 50, 60, and 70% of cement, by weight, was replaced by the high-lime and low-lime fly ash. For comparison, a control SCC mixture without any fly ash was also produced. The fresh properties of the SCCs were observed through, slump flow time and diameter, V-funnel flow time, L-box height ratio, U-box height difference, segregation ratio and the rheological parameters (relative yield stress and relative plastic viscosity). Relations between workability and rheological parameters were sought. Setting times and temperature rise of the SCC were also determined. The hardened properties included the compressive strength, split tensile strength, drying shrinkage and permeation properties (absorption, sorptivity and rapid chloride permeability tests) up to 360 days. The results obtained indicated that it is possible to produce SCC with a 70% of cement replacement by both types of fly ash. The use of high volumes of fly ash in SCC not only improved the workability and permeability properties but also made it possible to produce concretes between 33-40 MPa compressive strength at 28 days.

Concrete is by far the most widely used construction material worldwide in terms of volume, and so has a huge impact on the environment, with consequences for sustainable development. Portland cement is one of the most energy-intensive materials of construction, and is responsible for some emissions of carbon dioxide — the main greenhouse gas causing global warming. Efforts are being made in the construction industry to address these by utilising supplementary materials and developing alternative binders in concrete; the application of geopolymer technology is one such alternative. Indeed, geopolymers have emerged as novel engineering materials with considerable promise as binders in the manufacture of concrete. Apart from their known technical attributes, such as superior chemical and mechanical properties, geopolymers also have a smaller greenhouse footprint than Portland cement binders. / Research on the development, manufacture, behaviour and applications of low calcium fly ash-based geopolymer concrete has been carried out at Curtin University of Technology since 2001. Past studies of the structural behaviour of reinforced fly ash-based geopolymer concrete members have covered the flexural behaviour of members. Further studies are needed to investigate other aspects of the structural behaviour of geopolymer concrete. Design for both shear and bond are important in reinforced concrete structures. Adequate shear resistance in reinforced concrete members is essential to prevent shear failures which are brittle in nature. The performance of reinforced concrete structures depends on sufficient bond between concrete and reinforcing steel. The present research therefore focuses on the shear and bond behaviour of reinforced low calcium fly ash-based geopolymer concrete beams. / For the study of shear behaviour of geopolymer concrete beams, a total of nine beam specimens were cast. The beams were 200 mm x 300 mm in cross section with an effective length of 1680 mm. The longitudinal tensile reinforcement ratios were 1.74%, 2.32% and 3.14%. The behaviour of reinforced geopolymer concrete beams failing in shear, including the failure modes and crack patterns, were found to be similar to those observed in reinforced Portland cement concrete beams. Good correlation of test-to-prediction value was obtained using VecTor2 Program incorporating the Disturbed Stress Field Model proposed by Vecchio (2000). An average test-to-prediction ratio of 1.08 and a coefficient of variation of 8.3% were obtained using this model. It was also found that the methods of calculations, including code provisions, used in the case of reinforced Portland cement concrete beams are applicable for predicting the shear strength of reinforced geopolymer concrete beams. / For the study of bond behaviour of geopolymer concrete beams, the experimental program included manufacturing and testing twelve tensile lap-spliced beam specimens. No transverse reinforcement was provided in the splice region. The beams were 200 mm wide, 300 mm deep and 2500 mm long. The effect of concrete cover, bar diameter, splice length and concrete compressive strength on bond strength were studied. The failure mode and crack patterns observed for reinforced geopolymer concrete beams were similar to those reported in the literature for reinforced Portland cement beams. The bond strength of geopolymer concrete was observed to be closely related to the tensile strength of geopolymer concrete. Good correlation of test bond strength with predictions from the analytical model proposed by Canbay and Frosch (2005) were obtained when using the actual tensile strength of geopolymer concrete. The average ratio of test bond strength to predicted bond strength was 1.0 with a coefficient of variation of 15.21%. It was found that the design provision and analytical models used for predicting bond strength of lapsplices in reinforced Portland cement concrete are applicable to reinforced geopolymer concrete beams.

The master thesis deals with possibilities of utilization of conventional power plant fly ash after introduction of SNCR (Selective non-catalytic reduction) as a method of flue gas denitrification. Behaviour of fly ash containing products of denitrification, ash with water and stabilizate prepared from contaminated ash was studied. Experiments were focused on the study of various factors affecting the release of ammonia from prepared mixtures. Samples were exposed to the weather conditions to simulate deposition in addition to the laboratory experiment. Influence of the fly ash containing denitrification to mechanical properties and volume stability of pastes and mortars were also studied. The interaction of denitrification products with superplasticizers was studied on pastes. Achieved results were verified on concretes.

This thesis contains two parts: theoretical and experimental. In the theoretical part are described materials for production SCC and their effect on the properties of fresh and hardened concrete. Practical part is divided into two experiments. First experiment deals with the design, production and properties of hardened SCC strength classes C16/20, C20/25 and C25/30 with high volume fly ash and inert admixtures. The main endpoints were long-term compressive strength and modulus of elasticity. Second experiment of practical part deals with designs SCC with modulus of elasticity more than 40 kN/mm2.

L'objectif principal de cette thèse a été d'évaluer le potentiel de valorisation des cendres volantes de charbon issues de centrales thermiques Spreader Stoker (Cendres Volantes Spreader Stoker), dans la fabrication d'éco-ciments sur l'île de La Réunion. Nous avons dans un premier temps effectué une caractérisation physico-chimique des CVSS et vérifié leur réactivité. Deux voies de valorisation ont ensuite été retenues, l'une qui ne présente pas de valeur ajoutée mais qui permet de valoriser un volume important de CVSS par une stabilisation dans des matrices à base de ciment, l'autre qui offre une valeur ajoutée aux CVSS par une incorporation dans la fabrication de ciments composés. Le relargage en lixiviation a été étudié pour la première voie de valorisation retenue, puis, les effets des CVSS dans les matrices à base de ciment, notamment le rôle des imbrûlés contenus dans les cendres, ont été évalués aux états frais, durcissant et durci, suivi d'une petite exploitation numérique des données expérimentales. Enfin, une étude de durabilité sur des bétons à base de ciments de laboratoire a été faite par une approche comparative avec la pouzzolane naturelle, qui est actuellement utilisée pour la fabrication de ciments composés sur l'île de la Réunion. / The main objective of this project was to evaluate the potential of coal fly ash from Spreader Stoker thermal power plants (Spreader Stoker Coal Fly Ash) in the manufacture of eco-cements in Reunion Island. We first performed a physico-chemical characterization SSCFA and verified its reactivity. Two valorisation paths were chosen, one of which did not present any added value but which permit to value a large quantity of SSCFA by stabilization in cement-based matrices, the other which offers added value to SSCFA by incorporating it in the manufacture of composed cements. Leachate release was studied for the first path of valorisation, and then the effects of SSCFA in the cement matrices, especially the unburned particles contained in SSFCA, were evaluated in fresh, hardening and hardened states, followed by a small numerical exploitation of the experimental data. Finally, a sustainability study on concretes based on laboratory cements was made using a comparative approach with natural pozzolana, which is currently used for the manufacture of composite cements in Réunion Island.

O emprego de resíduos da indústria como materiais alternativos na Engenharia vem sendo tópico recorrente em pesquisas de desenvolvimento de novos materiais, devido a uma maior consciência da opinião pública quanto ao impacto ambiental oriundo da produção industrial. Buscando colaborar com esta discussão, esta pesquisa procurou inserir dois resíduos (cinza volante e cal de carbureto), gerados na região metropolitana de Porto Alegre, como alternativa de solução em Engenharia. Analisando-se a microestrutura da cinza volante, observa-se que ela é formada por esferas ocas e plerosferas (esferas ocas preenchidas por esferas menores). Foi estudado o ganho de resistência da mistura promovido pela moagem da cinza volante em um moinho de bolas cerâmicas, visando uma potencialização da reatividade do material. A fim de possibilitar a utilização destes resíduos, é necessário um estudo do seu comportamento mecânico decorrente da cimentação proporcionada pela mistura e compactação destes materiais. A presente pesquisa busca fornecer subsídios para que seja possível determinar o seu comportamento, através do uso da relação porosidade (η)/teor volumétrico de cal (LV) obtidas a partir da identificação e quantificação das variáveis mais importantes no controle da resistência da mistura dos dois resíduos, com e sem o processo de moagem da cinza, levando a formulação de equações para previsão da resistência à compressão simples do material cimentado para cinza volante com diferentes tempos de moagem e cura acelerada. Para isso, foram realizados ensaios de compressão simples em corpos de prova com 5, 10 e 15% de cal, com peso específico aparente seco de 11, 12 e 13 kN/m3, curados por 7 dias, com umidade de 18% para os tempos de moagem 0, 2 e 6h nas temperaturas 23 e 40°C, e 0 e 6h a 60°C. Os resultados apontam que o aumento do teor de cal gerou ganhos de resistência para as maiores temperaturas de cura; a diminuição da porosidade proporcionou um ganho de resistência para todas as combinações; o aumento da temperatura foi importante no ganho de resistência entre 23oC e 40oC; a moagem da cinza por 2h promoveu ganhos significativos de resistência em relação à não moída, porém, para 6h de moagem os ganhos não foram significativos para as temperaturas de cura de 23oC e 60oC. A relação η/LV, ajustada por um expoente [η/(Lv)0,07], mostrou-se adequada na formulação de equações na previsão da resistência do material cimentado para todas as temperaturas e tempos de moagem estudados. Além disso, a existência de relações únicas e distintas no controle da resistência à compressão simples em função da porosidade, teor volumétrico de cal, temperatura de cura e tempo de moagem, mostraram-se úteis para formulações de dosagem. Os resultados foram submetidos à análise de variância que comprovou que todos os fatores controláveis escolhidos para o experimento são significativos, assim como todas suas interações. / The use of industry by-products as alternative materials in Engineering has been a recurring topic of research in development of new materials, mainly, due to a larger public conscience regarding the environmental impact of industrial production of waste. Aiming to contribute on this discussion, this research sought to introduce two by-products (fly ash and carbide lime), produced on the metropolitan area of Porto Alegre, as an alternative Engineering solution. Analyzing the microstructure of the fly ash, it is observed that it is composed by void spheres and plerospheres (void spheres filed with smaller ones). Having that in mind, it was studied the admix strength gain promoted by the grinding of de fly ash on a ceramic ball mill, aiming an enhancement of the reactivity of the material. In order to enable the use of these byproducts, it is necessary the study of its mechanical behavior due to the cementation provided by the mixture and compaction of these materials. The current research seeks to provide subsides in order to determine its behavior, through the use of the ratio porosity (η)/ volumetric lime content (LV), obtained from the identification and quantification of the most important variables on the control of the strength of the admixes of both by-products, with or without the process of fly ash grinding. This means, the formulation of equations for the simple compressive strength forecast of the cemented material for the fly ash with different grinding times and accelerated curing temperature. In order to do so, it were realized simple compression tests with 5, 10 and 15% of lime, with a specific dry unit weight of 11, 12 and 13 kN/m3, cured for 7 days, with water content of 18% for the grinding times of 0, 2 and 6h to the curing temperatures of 23 and 40oC, and 0 and 6h to 60oC. The results show that, the increase of lime content provided strength gains for the higher temperatures; the decrease of porosity generated strength gain to all the combinations; the increase in curing temperature was important on the strength gain between 23oC and 40oC; the grinding of fly ash for 2h promoted significant strength gains when compared to the not ground samples, however, for 6h of grinding the strength gain wasn’t significant for the 23oC and 60oC curing temperatures. The η/LV ratio, adjusted by an exponent [η/(LV)0,07], presented itself adequate for the formulation of the equations for the forecast of the strength gain of the cemented material to all the studied temperatures and grinding times. Besides that, the existence of unique and distinct relationships on the control of the simple compression strength depending on the porosity, volumetric lime content, curing temperature and grinding time, have been shown useful for the dosage formulation. The results were submitted to variance analysis, which demonstrated that all the factors chosen on the experiment were significant, as all their interactions.

The thesis presents comparison anti-dustiness measures done on fly-ash deposits for several invertebrate groups colonising those deposits. To prevent dustiness, fly-ash is covered by a soil layer. The thesis compares number and abundance of species of any category of Czech Red List of Endangered Species, and species specialized on sandy biotopes on bare fly-ash, fly-ash patrially covered by a soil layer and fly-ash covered by soil layer completely. The consequence of results is that at least small patches of bare soil are crucial for rare species.