Building rammed earth structures provides a sustainable alternative to concrete. As a building material, rammed earth exhibits very varied physical and material properties depending on the proportion of constituting soil types. When very sandy soil is used in rammed earth production, the properties are different from when a clayey soil is used. This variability can be seen as a very great advantage in the use of rammed earth as a building material. Builders are able to adjust specific properties by changing mix proportions to obtain a desirable balance in the characteristics of the resulting rammed earth structure. This research work looks at selected mechanical and physical properties of different mixes of rammed earth. It describes typical range of values in density, thermal conductivity, ultrasonic pulse velocity, water ingress and compressive strength. It examines how these factors interrelate in the same soil mixes. Samples were prepared by blending various soil types in specific proportions to ensure that each definition of soil grade is as specific as possible. Unstabilised rammed earth was tested as was cement stabilised rammed earth. Rammed earth was tested at various levels of stabilisation and it was discovered that higher rates of stabilisation was not always beneficial to every material property. The research also looked into the potential disposal of waste materials in rammed earth. As rammed earth is a monolithic material that largely remains undisturbed throughout its life span, it was suggested that waste materials could be stored in an inert form inside of rammed earth rather than dumping it in otherwise agricultural landmass. Pulverised Fuel Ash and Palm Kernel Shells were identified as wastes to be disposed in rammed earth. Pulverised Fuel Ash, a by-product of industrial furnace is found in abundance in developed countries that burn carbonaceous materials in power plants. Disposals have been seen as a problem as only a small proportion of high loss on ignition (LOI) Pulverised Fuel Ash has found application. Palm Kernel Shell is a by-product of the oil palm industry and is currently a menace in many developing countries that need to dispose large quantities of the shell in landfills. At an early stage of the research, experimental trial runs quickly showed that these supposedly waste materials had a positive effect on some of the material properties of the rammed earth walls they were made into. This research effort evolved to look into exploiting these materials to improve the physical and material property of rammed earth and to suggest their effect on stabilised and unstabilised rammed earth. The extent to which these materials could be useful and the level at which diminishing returns set in was also investigated. It was discovered that soil mixes that would otherwise not be considered suitable for use in rammed earth wall production can now be utilised as their characteristics can be improved on simply by adding Pulverised Fuel Ash or Palm Kernel shell in the right proportion. Incorporating Pulverised Fuel Ash in rammed earth resulted in increased compressive strength. Palm Kernel shell improved thermal properties without compromising compressive strength.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The construction industry has been studying the possibility of using industrial subproducts, as a strategy to remedy the environmental matters, considering that the sub-products are generated in large quantities and mostly without specific destination. In the present study investigates the feasibility of using the RHA residual, natural or ground, in structural concrete, in partial replacement of Portland cement, from the analysis of durability characteristics of the concrete. However, some natural rice husk ash have natural expansive effect due to the reaction of silica under form of microcrystalline and the cement alkali. Thus, it justifies the use of fly ash, forming ternary mixtures, as the solution to mitigate the expansion generated by alkaliaggregate reaction (AAR) or alkali-silica (RAS). For this, three binders mixtures were tested: one composed with the RHA natural + FA, one with RHA ground + FA and the last one composed with a reference mixture 80% of Portland cement and 20% of FA, in which confronted the results. It was adopted the replacement levels of 15% of RHA, and the relations a/g of 0.45; 0.55 and 0.65. It was conducted the trials of apparent electrical resistivity, specific electrical conductivity, resistance to chloride penetration according to the method of accelerated penetration ASTM C1202 (EAPC). Additionally, the trials of axial compressive strength and water absorption by capillarity were performed, according to requirements of ABNT. The obtained results in the research confirm that is feasible to use the residual RHA, natural or ground, as partial replacement of Portland cement, in concrete for structural use. It was found that the age and the ratio a/g showed a significant influence on the electrical resistivity and electrical conductivity of concrete, mainly due to changes in pore structure and the quantity and composition of them solution, showing there is a great correlation among these factors. As for the axial compressive strength, at 182 days, the mixture composed with RHA ground presented higher performance than to the reference mixture. However, for the mixing with RHA natural, the same course was not observed. In the EAPC the use of RHA ground, burned without temperature control, resulted in lower values of loads bystanders and lowest penetration depths, when compared to the mixtures with RHA natural and of reference. In the case of water absorption by capillarity, it was found that the use of RHA, in general, decreased the water absorption of concrete. / A indústria da construção civil vem estudando a possibilidade da utilização de subprodutos industriais, como uma das ações para solucionar as questões ambientais, tendo em vista que os mesmos são gerados em grandes quantidades e na sua maioria sem destinação específica. No presente trabalho investiga-se a viabilidade de se utilizar a CCA residual, ao natural ou moída, em concretos estruturais, em substituição parcial ao cimento Portland, a partir da análise de características de durabilidade do concreto. Porém, algumas cinzas de casca de arroz naturais apresentam efeito expansivo devido à reação entre a sílica sob a forma microcristalina e os álcalis do cimento. Assim, justifica-se o uso da cinza volante, formando misturas ternárias, como a solução para mitigar a expansão gerada pela reação álcali-agregado (RAA) ou álcali-sílica (RAS). Para isso, foram testadas três misturas aglomerantes: uma composta com CCA ao natural + CV, uma com CCA moída + CV e uma mistura de referência com 80% cimento Portland e 20% de CV, a qual se confrontaram os resultados. Adotou-se o teor de substituição de 15% de CCA, e as relações a/ag de 0,45; 0,55 e 0,65. Procederam-se os ensaios de resistividade elétrica aparente, condutividade elétrica específica, resistência à penetração de cloretos segundo o método de penetração acelerada ASTM C1202 (EAPC). Adicionalmente, foram realizados os ensaios de resistência à compressão axial e de absorção de água por capilaridade, segundo prescrições da ABNT. Os resultados obtidos na pesquisa confirmam que é viável utilizar a CCA residual, ao natural ou moída, como substituição parcial ao cimento Portland, em concretos para uso estrutural. Verificou-se que a idade e a relação a/ag mostraram uma influência expressiva na resistividade elétrica e condutividade elétrica do concreto, em virtude principalmente das alterações na estrutura dos poros e na quantidade e composição da solução dos mesmos, mostrando haver uma ótima correlação entre estes fatores. Quanto a resistência à compressão axial, aos 182 dias, a mistura composta com CCA moída apresentou desempenho superior ao da mistura de referência. Porém, para a mistura com CCA natural, o mesmo comportamento não foi verificado. No EAPC a utilização de CCA moída, queimada sem controle de temperatura, resultou em valores de cargas passantes mais baixos e profundidades de penetração menores, quando comparados aos das misturas com CCA natural e de referência. No caso da absorção de água por capilaridade, constatou-se que a utilização de CCA, em geral, diminuiu a absorção de água dos concretos.

The aim of this thesis is to summarize the knowledge regarding reduction of negative impact of high volumes of fly ash in HVFA concretes using nanotechnology and experimentally verify the findings. To compensate the inferior early-age properties, it is possible to use active nanoparticles, such as nanosilica or nanolimestone. The first step of the experiment was the production of stable nanoparticle’s dispersions using ultrasonic homogenization and UV/Vis spectroscopy. In subsequent steps the influence of nanoparticle’s presence on cementitious materials’ properties was verified on cement pastes and mortars with 40 a 60 % of fly ash. The best variant was then used to produce nano-modified HVFA concretes. Even at a minimum dose, the positive effect on early-age properties indicates the usefulness of nanoparticles in technology of concrete. An important contribution of this thesis is also the acquired knowledge related to the nanoparticle’s behavior and handling.

Abstract Biomass, such as wood, binds CO2 as it grows, and is thus considered an environmentally friendly alternative fuel to replace coal. In Finland, biomass is typically co-combusted with peat, and also municipal waste is becoming more common as a fuel for power plants. Wood, peat and waste-based fuels are typically burned in fluidized bed combustion (FBC) boilers. Ash is the inorganic, incombustible residue resulting from combustion. The annual production of biomass and peat ash in Finland is 600 000 tonnes, and this amount is likely to increase in the future, since the use of coal for energy production will be discontinued during the 2020s. Unfortunately, FBC ash is still largely unutilized at the moment and is mainly dumped in landfills. The general aim of this thesis was to generate information which could potentially improve the utilization of FBC ash by alkali activation. The specific objective was to produce geopolymer aggregates by means of a simultaneous alkali activation-granulation process. It was shown that geopolymer aggregates with physical properties comparable to commercial lightweight expanded clay aggregates (LECAs) can be produced from FBC fly ash containing heavy metals. Although the ashes were largely unreactive and no new crystalline phases were formed by alkali activation, a new amorphous phase was observed in the XRD patterns, possibly representing micron-sized calcium aluminate silicate hydrate-type gels. The heavy metal immobilization efficiency of alkali activation varied with the type of fly ash. Good stabilization was generally obtained for cationic metals such as Ba, Pb and Zn, but in common with the results obtained with alkali activation of coal fly ash, anionic metals became leachable after alkali activation. The efficiency of immobilization depended on the physical and chemical properties of the fly ash and was not related to the total content of the element. All the geopolymer aggregates met the criteria for a lightweight aggregate (LWA) as defined by EN standard 13055-1. Their strength depended on the reactivity and particle size distribution of the fly ash. Mortars and concretes prepared with such geopolymer aggregates had higher mechanical strength, higher dynamic modulus of elasticity and higher density than concrete produced with commercial LECA, while exhibiting similar rheology and workability. / Tiivistelmä Biopolttoaineet, esimerkiksi puu, ovat ympäristöystävällinen vaihtoehto kivihiilelle, koska ne sitovat hiilidioksidia kasvaessaan. Suomessa biopolttoaineita poltetaan tyypillisesti turpeen kanssa, ja nykyään myös jätteen hyödyntäminen polttoaineena on yleistynyt. Puu, turve ja jätepolttoaineet poltetaan tyypillisesti leijupetipoltto-tekniikalla. Tuhka on polton epäorgaaninen, palamaton jäännös. Puun ja turpeen tuhkaa tuotetaan Suomessa 600 000 tonnia vuodessa ja määrän odotetaan kasvavan, sillä kivihiilen poltto lopetetaan 2020-luvulla. Leijupetipolton tuhkaa ei tällä hetkellä juurikaan hyödynnetä ja tuhka päätyykin pääasiassa kaatopaikoille. Tämän tutkielman päämääränä oli tuottaa tietoa, joka parantaisi leijupetipolton tuhkien hyödyntämistä alkali-aktivaatiolla. Erityisesti tavoitteena oli valmistaa geopolymeeriaggregaatteja yhtäaikaisella alkali-aktivaatiolla ja rakeistuksella. Tutkielmassa osoitettiin, että raskasmetalleja sisältävistä tuhkista valmistettujen geopolymeeriaggregaattien fysikaaliset ominaisuudet ovat vertailukelpoiset kaupallisten kevytsora-aggregaattien (LECA) kanssa. Vaikka tuhkien reaktiivisuus oli matala, ja uusia kidefaaseja ei muodostunut alkaliaktivaatiolla, uusi amorfinen faasi havaittiin XRD-mittauksissa. Uusi amorfinen faasi oli mahdollisesti mikrometrikokoluokan kalsium-aluminaatti-silikaatti-hydraatti-tyyppinen rakenne. Raskasmetallien stabiloinnin tehokkuus vaihteli tuhkien välillä. Kationiset metallit, kuten barium, lyijy ja sinkki, stabiloituivat pääasiassa hyvin, mutta anionisten metallin liukoisuus kasvoi alkali-aktivoinnin myötä. Stabiloinnin tehokkuus riippui tuhkien fysikaalisista ja kemiallisista ominaisuuksista, mutta raskasmetallin kokonaispitoisuudella ei ollu vaikutusta. Kaikki geopolymeeriaggregaatit olivat kevytsora-aggregaatteja standardin EN 13055-1 mukaisesti. Aggregaattien lujuus riippui tuhkan reaktiivisuudesta ja partikkelikokojakaumasta. Geopolymeeriaggregaateilla valmistettujen laastien ja betonien mekaaninen lujuus, Youngin moduuli ja tiheys olivat korkeampia kuin kaupallisella kevytsora-aggregaateilla valmistetut, vaikka niiden reologia ja työstettävyys olivat samanlaisia.

Thermal power station in most countries is saddled with the problem of fly ash disposal and unless suitable avenues are found for its proper use, this would pose a gigantic problem to the power sector. Disposal of huge quantities of fly ashes without proper care causes considerable impact on the environment particularly the one leading to soil and groundwater contamination. On the other hand, fly ashes have many desirable properties which can find applications in civil engineering, especially in geotechnical engineering. The pozzolanic reactivity is one of the important properties of fly ashes that enhance its application. Thought the fly ashes with self – pozzolanic property are well utilized, fly ashes with insufficient free lime, such as class F fly ashes are being grossly underutilized and they form a considerable portion of fly ashes that are disposed. Yet another factor restricting the use of fly ash is the concern about the leachability of lime under field conditions particularly under saturated or partially saturated conditions. Hence an attempt is made in this thesis, to reduce the lime leachability of class F fly ashes with different additives. Thus, selection of right amounts of additives to reduce the lime leacability is an important aspect studied in this thesis. Effect of such as strength, compressibility, and CBR value is also investigated. Another simple way to reduce the problem of disposal of fly ash is to utilize it for the construction of waste disposal sites particularly for lining solid waste disposal facilities in place of the natural clay materials which are very often procured by excavating and transporting from far off places. Also, the capacities of fly ashes to sorb heavy metal that are likely to be present in the leachates generated from the industrial wastes have been studied. Of the other factors limiting the generous use of fly ashes is the leachability of several trace elements present in them. Hence the leachability of trace metals from fly ashes under different practical situations, before and after incorporating the selected additives for improving the engineering properties of fly ashes, has been studied. The thesis is presented in 10 chapters. The relevant background for the studies and scope of the work is given Chapter 1. Sources of the fly ashes collected for the investigating along with their physical and chemical properties are presented in chapter 2. Two low line fly ashes are collected directly from the electronic precipitators of the thermal power plants located at Neyvelli town of the Tamil nadu and Maddanur town of Andhra Pradesh, India, named NFA and MFA respectively. MFA has greater finer particle content than NFA. The particles of MFA Have rougher surface compared to those of NFA. Both of fly ashes have predominantly quartz and mullite phase in them. The silica, total lime and carbon contents which have major influence on the pozzolanic reactivity of fly ashes vary considerably in the both the fly ashes. Lime leachability is taken as the amount of lime that is converted into soluble form (by dissociation into calcium and hydroxyl ions) under a standardized condition. It can be used to asses the long term sustainability of the strength achieved in fly ashes with lime. Lime leachability studies have been conducted on the fly ashes stabilized with different additives in specially designed moulds. Results presented in Chapter 3 showed that leachability of lime in fly ashes increases with the increase in lime content though it is not in proportion to the increase in lime content. This is because the solubility of lime is less and is independent of the total lime present. The marginal reduction in leachability is mainly due to cemented matrix of fly ash inhibiting the leaching of time. The higher the strength of the matrix the lower is the leachability. Further it is made clear that at any lime content presence of gypsum reduces the time leachability which has been attributed to the transformation of pozzolanic compounds into less soluble form than the compounds formed with lime alone. With the increase in curing period, the amount of lime that leaches from the lime-stabilized fly ashes as well as those treated with gypsum to a considerable extent. The nature of alteration does not seem to change with time as revealed by a good correlation between lime leachability ratios obtained after 7 days and 14 days of curing periods. Chapter 4 presents the results of unconfined compressive strength tests carried out on fly ashes with varying lime and gypsum contents, before soaking and also soaking in several heavy metal solutions, along with the durability to the cycle of wetting and drying. The results revealed that the strength of low lime fly ashes increases with lime content significantly up to the optimum lime content of about 2.5 – 5% and gradually thereafter. Addition of gypsum of 1 – 2.5% increases the strength of fly ashes further at any lime content. Increase in strength with gypsum, which is quite significant at lower lime contents initially, is observed for a considerable period (up to 180 days) at higher lime contents. The increase in strength is as high as 40-fold in some instances. This increase in strength which is also more durable has been attributed to the formation of calcium – sodium – aluminium - silicate hydrate along with calcium silicate hydrate. Further, it is observed that fly ash which responds better to lime stabilization shows accelerated gain in strength due to the addition of gypsum at early curing periods than the fly ash that responds solely to lime. Decrease in lime leachability ratio is a good indication of the increased strength along with the increased durability. California Bearing Radio (CBR) values are of great significance in the utilization of fly ashes in bulk quantities for the construction of road and railway embankments and pavements. Studies conducted to determine the CBR values of fly ashes with different lime and gypsum contents after curing for different time periods are described in chapter 5. The CBR values are observed to increase with lime alone significantly up to 2.5% and only marginally beyond. But the increase in CRB values is considerable with gypsum at any lime content. The increase in CBR value is particularly more with 2.5% gypsum for fly ashes with 2.5% lime. The CBR values of stabilized fly ashes are generally higher for 5 mm depth of penetration than those for 2.5 mm one due to the high stiffness of the matrix formed even at low strain levels. The loss in CBR values with soaking is relatively more at lower curing the periods due to the improper cementation of particles. Even after this significant loss in CBR values, fly ashes with 2.5% lime and 2.5% gypsum register the maximum values after curing under soaked condition. Unlike in the case of unconfined compressive strength, lime leachability values could not be well correlated with the CBR values of fly ashes with different lime and gypsum contents since many more factors influence the CBR values than those of unconfined compressive strength alone. Chapter 6.brings out the effects of addition of lime alone and lime along with gypsum on the compressibility behaviour of the fly ashes. Since the fly ashes when treated with additives develop strength and exhibit lower compression with the passage of time, consolidation testing with conventional duration of load increment may not be appropriate. Hence an attempt has been made to assess the minimum duration of load increment necessary to study the compressibility characteristics of such materials. Thus the compressibility behaviour of fly ashes with additives has been studied using conventional consolidation test with different durations of load increments varying from 30 minutes to 48 hours. The results indicated that 30 minutes of duration of load increment can be used to assess the compressibility behaviour of such materials. The effect of lime which reduces the compression is seen to be maximum from the results obtained with the load duration increment of 30 minutes but gradually reduce with higher duration of load increment. It has also been observed that the rate of decrease in the compressibility is maximum up to 2.5% lime and thereafter gradual. The compressibility of lime –treated fly ashes further reduces when gypsum is incorporated, the optimum gypsum percentage being 2.5. This reduction in the compressibility of fly ashes enhanced by incorporating lime and gypsum makes them versatile in the construction of embankments and for structural fills, particularly reducing the time required in between laying of each lift. It has been brought out that decrease in the lime leachability decreases the compressibility of fly ashes. Fly ash has potential application in the construction of base liners of waste containment facilities. While most of the fly ashes improve in the strength with curing, the ranges of hydraulic conductivities they attain may often not meet the basic requirement of a liner material. Attempts to reduce the hydraulic conductivity by adding lime as gypsum along with lime to both the fly ashes are presented in chapter 7. Hydraulic conductivities of the compacted specimens have been determined in the laboratory using the falling head methods. It has been observed that the addition of gypsum reduces the hydraulic conductivity of the lime treated fly ashes. The reduction in the hydraulic conductivity of the fly ashes containing gypsum is significantly more of sample with high amounts of lime contents (as high as 1000 times) than those with lower amounts of lime. However, there is relatively more increases in the strengths of the samples with the inclusion of gypsum to the fly ashes even at lower lime contents. This is due to the fact that excess lime added to fly ash is not effectively converted in to pozzolanic compounds. Even the presence of gypsum is observed not to activate these reactions with excess lime. On the other hand the higher amount of lime in the presence of gypsum is observed to produce more cementitious compounds which block the pores in the fly ash. Amount of lime leached in the found to be directly related to the hydraulic conductivity inspite of many –fold variations in the hydraulic conductivity achieved by curing fly ash with lime and gypsum. The consequent reduction on the hydraulic conductivity of fly ash would be beneficial in reducing the leachability of trace elements in the fly ash when used as base liner. Fly ash contains trace metals and other substances in the sufficient quantities which may leach out over a period of time. The study has been extended to examine the leachability of a few selected trace metals viz., Cd, Cu, Cr, Mn, Pb and Zn from fly ash before and after incorporating additives has been reported in chapter 9. The standard laboratory leaching test for the combustion residues developed by Van der Sloot et al. has been employed to study the leachabilities of trace elements as a function of liquid to solid (L/S) ratio and pH. The leachability test were conducted on the powdered fly ash samples obtained from unconfined compressive strength tests, conducted after a curing period of 28 and 180 days. It observed that, there is a marked reduction in the relative leachabilities of trace elements present, at the end of 28 days which reduced only marginally at the end of 180 days. Chapter 9 reports the retention capacities of fly ashes for copper, lead and zinc metals ions. Various parameters like contact time, initial concentration and pH have been varied and their effect on retention mechanism studied. The retention order of metals ions, Cu+ 2 > Pb+2>Zn+2, is observed to be the same for both the fly ashes at all pH values. The dominant mechanisms responsible for the retention are precipitation at higher pH’s as hydroxides and adsorption at lower pH’s Due to presence of silica and alumina oxide surface in fly ash. First order kinetic plots have revealed that the rate constant value increases with increase in initial concentration and pH. Langmuir adsorption isotherms have been plotted to study the maximum adsorption isotherms have been plotted to study the maximum adsorption capacities for metal ions under different conditions. The older indicates that the adsorption is predominantly by silica surface than that by alumina or iron oxide surfaces. This thesis demonstrates that incorporation of gypsum along with lime in the optimal proportions not only reduces the lime leachability but also greatly enhances the strength and CBR values, reduces the compressibility and minimizes the leaching of trace elements present in them enhancing the potential of fly ashes for many applications. Detailed conclusions are presented in chapter 10. The study greatly helps in promoting the use of fly ashes for many geotechnical and geo-environmental applications.

Philosophiae Doctor - PhD / 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. / South Africa

Nesta dissertação foi estudada a zeólita sintetizada a partir de cinzas leves de carvão como um potencial adsorvente para a remoção de corante reativo preto 5 (RP5). Ensaios cinéticos e de equilíbrio foram realizados visando obter-se as melhores condições para a adsorção deste corante, e verificou-se a influência dos seguintes parâmetros: efeito do tempo de contato, concentração inicial do corante, dose do adsorvente, pH da solução aquosa, adição dos sais NaCl e Na2SO4 e temperatura. O tempo de equilíbrio foi alcançado após 420 min. Os dados de adsorção foram ajustados melhor ao modelo cinético de pseudo-segunda-ordem. Para o sistema corante/adsorvente foi aplicado o modelo de isoterma de adsorção de Langmuir, apresentando capacidade de adsorção máxima de 0,685 mg g-1. Os dados experimentais mostraram uma alta porcentagem de remoção de 47,7 a 88,1% de RP5 sobre a zeólita. A alta porcentagem indicou que o material zeolítico apresenta potencial para ser usado como adsorvente na remoção de corantes azo reativo de indústrias têxteis. Os parâmetros termodinâmicos foram avaliados e demonstraram que o processo de adsorção do RP5 sobre a zeólita é espontâneo e exotérmico. Os experimentos adicionando os sais foram realizados para uma melhor simulação das condições reais do efluente. Os resultados mostraram que o equilíbrio de adsorção do RP5 sobre a zeólita na presença de sais foram alcançados em um tempo menor e que quanto maior a concentração dos sais na solução, maior a capacidade de adsorção. O resultado obtido na avaliação da toxicidade pelo microcrustáceo Daphnia similis, o tratamento de adsorção com zeólita se mostrou extremamente favorável5 reduzindo a carga tóxica e cor do efluente aquoso. / In this dissertation was studied the zeolite synthesized from coal fly ash as a potential adsorbent for the removal of reactive Black 5 dye (RP5). Equilibrium and kinetic experiments were conducted to obtain the best conditions for the adsorption of this dye, and observed the influence of the following parameters: effect of contact time, initial dye concentration, adsorbent dose, pH of the aqueous solution, addition of NaCl and Na2SO4 and temperature. The equilibrium time was reached after 420 min. The adsorption data were fitted better by a pseudo-second-order. For the dye / adsorbent system was applied to the model of Langmuir adsorption isotherm, with maximum adsorption capacity of 0.685 mg g-1. The experimental data showed a high percentage of removal from 47.7 to 88.1% of RP5 on the zeolite. The high percentage indicates that the zeolitic material has a potential to be used as adsorbent in the removal of azo dye reactive textile industries. The thermodynamic parameters were evaluated and showed that the adsorption process of RP5 on the zeolite is spontaneous and exothermic. The experiments were performed by adding salts to better simulate actual conditions in the effluent. The results showed that the adsorption equilibrium of reactive black 5 on the zeolite in the presence of salts were achieved in a shorter time and that the higher the concentration of salts in solution, the higher the adsorption capacity. The result obtained in the evaluation of toxicity by microcrustacean Daphnia similis treatment with zeolit adsorption was extremely favorable, reducing the toxic load of waste water and color.

Rare earth elements (REEs) are critical materials in many electronics and green technology products. Though the demand for REEs is growing rapidly, China controls over 90% of the REEs supply and the US currently is not producing any REEs. As most of the REEs occurred together in the mineral ores with low concentrations and they have similar chemical and physical properties, the extraction and purification processes are challenging. Conventional methods for producing REEs require large amounts of toxic chemicals and generate large amounts of hazardous wastes. Therefore, it is important to develop alternative REE sources as well as efficient and environmentally friendly processes to produce REEs domestically. In this dissertation, coal fly ash, a major coal combustion byproduct, was explored as a potential source for REEs. Novel separation and purification methods were developed for producing high purity REEs from class F coal fly ash.<div><br></div><div>First, a sequential separation process was developed to recover and concentrate REEs from class F coal fly ash. The ash was first digested using a NaOH solution and subsequently dissolved in an acid to extract REEs as well as other chemicals. About 74% of REEs, 92 % of SiO2, 74% of Al2O3, 24% of Fe2O3, and 65% of CaO were extracted. Most (>99%) of the extracted REEs and cations (Al+3, Fe+3, Ca+2) were captured in a cation exchange column. Negatively charged Si species were eluted by water. The captured REEs were separated from the other cations in the column. A solution of NaCl was used to elute the cations and most of the REEs, which were strongly adsorbed in the column, were eluted using a solution of diethylenetriaminepentaacetic acid (DTPA). In this separation process, high purity SiO2 (>99%), Al(OH)3 (>99%), and Fe(OH)3 (>95%) were produced. The eluted DTPA-REEs solution was then loaded in a cation exchange column. The REEs accumulated in the column could be further separated into pure REE fractions using a ligand-assisted displacement chromatography method (LAD), instead of the conventional liquid-liquid extraction method.<br></div><div><br></div><div>Detailed rate model simulations were developed for LAD and verified with experimental and literature data. The dynamic column profiles in simulations showed that a prestaurant which has a higher ligand affinity and a lower sorbent affinity than REEs is required to develop an isotachic train in LAD. When a constant-pattern isotachic train is developed, high concentration bands with high purity and high yield can be achieved. Further increase in column length is not needed. Thus, if purity, yield, sorbent, and ligand are fixed, the constant-pattern state gives the highest sorbent productivity and the highest ligand efficiency. It is critical to develop a method to find the general conditions required for developing constant-pattern states. Key dimensionless parameters affecting the constant-pattern states were formulated first based on the h-transformation theory for an ideal system and the shock layer theory for a nonideal system. Strategetic combinations of the key dimensionless groups were developed to express a dimensionless mininum column length as a function of the combined dimensionless groups. Rate model simulations were used to find various minimum column lengths for developing constant-pattern states from transient states. The simulation results were used to generate a correlation curve in a two-dimensional plot or map where the curve divided the map into two regions, the transient region, and the constant-pattern region. The map can be used to find the minimum required conditions for developing a constant-pattern state for a general LAD system at any scale.<br></div><div><br></div><div>A constant-pattern design method for both ideal and non-ideal (with significant mass transfer effects) LAD systems was developed based on the general correlation equation for the map. In addition, an equation for the yield of a target component as a function of the key dimensionless groups was derived based on the constant-pattern mass transfer zone lengths. The column length and operating velocity solved from the two equations ensured the yields and the constant–pattern state for the target components. A selectivity weighted composition factor was developed to allow the design method to specify a minimum target yield for one or multiple components. The design method is robust and scalable because it provides the optimal operating conditions to meet the minimum target yield and purity of one or multiple components for LAD systems at any scale. The design method was verified using simulations and experiments for different target yields, ligand concentrations, and feed compositions for ternary mixtures. The minimum target yields were achieved or exceeded in all cases tested. The results showed that high ligand concentration, long column length, and high effective sorbent selectivity can increase sorbent productivity. The minimum column length required to achieve a constant-pattern state and the productivity of LAD are limited by the lowest selectivity or by a minority component with a low concentration in the feed, even when it does not have the lowest selectivity. If both minor and major REE components in a mixture need to be recovered in the same LAD process, the overall productivity could be significantly limited. Thus, separating major components first and recycling/separating the minor components in a separate LAD process could increase the total productivity significantly. The productivities achieved using this design method are two orders of magnitude higher than the literature results with similar REE yields and purities.<br></div>

Philosophiae Doctor - PhD / Coal combustion accounts for 95% of electricity generation in South Africa while globally coal combustion for energy generation stands at 42%. It has been predicted that coal utilization for energy generation will continue due to its low cost and availability in huge quantities in different parts of the world. Additionally brine and gaseous emissions are produced in the power generation and coal combustion processes. In fact, it has been established that CO2 emissions from power plants are the main cause of the green-house effect leading to global warming. Mitigation of the effects of disposal of fly ash, brine and CO2 emissions is critical for sustainable energy generation from coal and environmental protection. The study investigated whether South African coal fly ash could be used for brine remediation and CO2 capture using fly ash based hydrotalcites and zeolites. Four main objectives were investigated. These were; firstly, to compare the natural CO2 capture potential of a power station ash dam with an accelerated ex-situ mineral carbonation process. Secondly, to probe the effect of accelerated ex-situ mineral carbonation on brine quality with regards to major, minor and trace elements concentration. Furthermore, the study investigated the feasibility of synthesizing hydrotalcites from fly ash by optimizing the synthesis parameters such as acid concentration, aging time, aging temperature, pH during aging, crystallization time and crystallization temperature. Finally the study compared the CO2 adsorption capacities of the fly ash based hydrotalcites with fly ash based zeolites NaA, and NaX. The natural carbonation potential of the wet disposed ash dam at Secunda was investigated by coring a 20 year old dam. Three cores (SI, S2 and S3) were obtained by air flush coring the dam along a geophysical line and establishing the geophysical profile of the three cores. The surface of the three cores was of medium resistivity with values between 9.3 and 12.2 nm while the midsections were of low resistivity with values ranging between 4 and 7 nm. The base section of core SI had a resistivity of 28.3 nm, that of S2 was between 16.2 and 21.4 nm and that of S3 between 12.2 and 16.2 nm; implying that SI had the lowest salt load while S3 had the highest salt content. Moisture content was observed to be high deeper down the profiles of S2 and S3 with samples appearing water logged while SI had the highest moisture content at the surface showing the inhomogeneity of the ash dam. The morphology of fresh fly ash taken from the ash collection hoppers at Secunda was observed to be spherical. Weathered ash from the ash dam showed irregularly agglomerated particles while accelerated ex-situ mineral carbonation resulted in the formation of acicular particles of calcite. Fresh ash, weathered ash and the accelerated carbonated ash were all class F with a sum total of silica, alumina and iron oxide totaling more than 70%. A reduction in silica and alumina content with instability of fly ash. Dumping of spent iron catalyst (resulting from the petrochemical operations as Sasol) on the ash dam led to an increase in Fe203 content of the weathered ash. Enrichment of Nb, Sr, Y, Th, Na, Cl, S04, K and S with natural carbonation as well as during accelerated ex-situ mineral carbonation was observed and was due to the contact of ash with brine during these two processes. Reduction of Zr, Rb, Pb, Ni, Co and V content of ash was observed with weathering. Mineralogically, all the ash samples had main phases of mullite, quartz, magnetite and hematite, with weathered and accelerated carbonated ash having additional phases of calcite. The aluminosilicious nature of the three ashes was identified by structural evaluation using Fourier transform infrared analysis which revealed that, bands associated with C-O in-plane and out of plane bending of carbonates was only visible in weathered and carbonated ash.

The thesis is focused on research and development of hydraulic binders based on FBC-ashes. It examines the possibilities of using this ash in the clinker so that the properties of the final cement are comparable to Portland cement. As an integral part of this thesis the research of emission reduction possibilities in the cement industry - a very current topic these days - is presented.