A crescente necessidade de se obter fontes de energia e materiais mais sustentáveis tem aumentado o interesse em processos baseados na conversão de biomassa. Microalgas são particularmente interessantes por não competirem com alimentos e serem facilmente adaptáveis ao meio de crescimento. Além disso, microalgas podem ser processadas termicamente para geração tanto de biocombustíveis quanto de produtos químicos úteis. Estudos de conversão térmica de microalgas tem aparecido apenas em anos recentes, endereçando principalmente temperaturas entre 350 e 500 ºC. Neste estudo, a pirólise em temperaturas entre 500 e 900 ºC foi avaliada pelo interesse em se obter biocombustíveis e produtos químicos úteis. As classes de compostos obtidos a partir da pirólise isotérmica da microalga da espécie Chlorella vulgaris foram investigadas através de um sistema composto por um pirolisador conectado a um CG/MS. Dentre as classes identificadas, houve uma predominância de compostos aromáticos e nitrogenados, principalmente derivados de proteínas. Além disso, a maioria dos compostos identificados na corrente de produtos voláteis está presente em todas as temperaturas de reação estudadas. Os parâmetros cinéticos de energia de ativação aparente, constante de reação e ordem de reação foram determinados através de três modelos cinéticos conhecidos como K-A-S, Osawa e Freeman-Carroll, a partir de dados termogravimétricos. A energia de ativação determinada para Chlorella apresentou valores entre 60 e 206 kJ/mol, enquanto a ordem de reação teve como resultado valores entre segunda e décima ordem, de acordo com o modelo cinético. / The increasing need to obtain more sustainable sources of energy and raw materials has attracted attention to processes based on biomass conversion. Microalgae are particularly interesting because they do not compete with human food and they are easily adaptable to the growth medium. Besides, microalgae can be thermally processed to produce both biofuels and useful chemicals. Studies on thermal conversion of microalgae have appeared only in recent years, addressing mainly reaction temperatures between 350 and 500 °C. In this study, pyrolysis in temperatures ranging from 500 to 900 ºC have been investigated considering the interest in producing biofuels and useful chemical compounds. The classes of products obtained by isothermal pyrolysis of the Chlorella vulgaris microalgae have been investigated using a pyrolyzer directly connected to a GC/MS system. Among the classes identified, there was a predominance of aromatic and nitrogenous compounds, mainly protein derived compounds. In addition, most products identified in the volatile products stream are present in all reaction temperatures investigated. The kinetic parameters of apparent activation energy, reaction constant and order of reaction were determined through three kinetic models known as K-A-S, Osawa and Freeman-Carroll, calculated from thermogravimetric data. The activation energy for Chlorella presented values within the range of 60 and 206 kJ/mole, while the order of reaction resulted in values between second and tenth order, from the different methods.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Persisting challenges associated with remediation of heavy metals from aqueous media have stirred the need for enhancement of current technologies. Cellulosic agro waste materials (AWM) as well as ion-imprinted polymers (IIP) have received ardent attention from researchers. These materials are often employed in the following industries: water and wastewater treatment, medical, pharmaceutical and packaging. Applications in water and wastewater treatment have gained significant interest due to desirable features they possess. In the case of AWM, these features include a tuneable surface area and poor porosity, basic surface functional groups and chemical stability. Some desired features in IIP include adsorption sites compatible for the ion imprint obtained after leaching with suitable reagents, rigidity and reusability. The efficacy of employing AWM and IIP for the remediation of toxic chromium from aqueous solution was explored. The current study is made up of part A and B. In part A, Macadamia nutshell powder was treated using HNO3, NaOH, as well as Fenton’s reagent. The three materials underwent a new modification which involved reacting treated adsorbents with cetyltrimethylammonium chloride (CTAC), followed by immobilization of 1,5' diphenylcarbazide (DPC) ligand. The adsorbents were ultimately washed, dried and stored for Cr(VI) batch adsorption experiments. Part B involved a synthesis of IIP and their non-imprinted polymer counterpart (NIP) for Cr(VI) sequestration in aqueous solution. This was done by precipitation polymerization of functional monomers, crosslinker and DPC-Cr(VI) complex as a template. Non-imprinted polymers were fashioned in a manner like that of IIP but with the exclusion of Cr(VI) ion template. Characterizations of the adsorbents were done using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen and sulphur (CHNS) analyzer. Batch adsorption experiments were done and parameters such as solution pH, adsorbent dosage, initial Cr(VI) concentration and contact time were optimized. Working solutions were analyzed using ultraviolet-visible (UV-Vis) and atomic absorption (AA) spectroscopy. Adsorption parameters found to be optimum for DPC immobilized cellulosic adsorbents were pH 1.4, adsorbent mass of 0.1 g, 100 mg/L initial concentration and 125 minutes of contact time. The adsorption parameters determined to be optimum for IIP and NIP were pH 2.6, 0.2 g adsorbent mass, 80 mg/L initial concentration and 240 minutes of contact time. Reusability studies demonstrated the potential of adsorbents to remove Cr(VI) ions from aqueous media after successive adsorption-desorption cycles. Selectivity studies indicated that DPC immobilized adsorbents as well as IIP were able to selectively adsorb Cr(VI) ions from aqueous media in the presence of Zn(II), Cu(II), Co(II) and NI(II) ions. Kinetic models revealed that DPC immobilized cellulosic adsorbents and synthetic IIP were most fitting for pseudo-second order and pseudo first order, respectively. On the other hand, adsorption isotherm studies demonstrated that DPC immobilized cellulosic adsorbents and synthetic polymers were best fit for Freundlich and Langmuir adsorption isotherm, respectively.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Agricultural waste such as Macadamia nutshells are currently receiving more attention for removal of hexavalent chromium (Cr(VI)). However, they have low adsorption capabilities when used in their raw form. In this study, the efficiency of using Macadamia nutshell powder modified with different concentrations of hydrogen peroxide, grafted with 1,5’-diphenylcarbizide (DPC) for the removal of hexavalent chromium from aqueous solution was explored. The effects of various parameters controlling adsorption of Cr(VI) onto Macadamia adsorbents such as initial concentration, contact time, adsorbent concentration and pH were investigated. The optimal operating parameters for Macadamia nutshells treated with hydrogen peroxide (MHP) adsorbents were determined to be 75 mg/L, 3 h, 0.1 g and pH 1. The optimal operating parameters for Macadamia nutshells treated with hydrogen peroxide and grafted with 1,5’-diphenylcarbizide (MHPD) were determined to be 150 mg/L, 1 h, 0.1 g and pH 3. Fourier transform infrared (FTIR) spectroscopy of the adsorbents revealed that treated MHP showed amino groups attached to the adsorbents. Thermogravimetric analysis (TGA) revealed that the grafted material lowered the thermal stability from 180◦C to 300◦C due to volatile nature of DPC. The surface of the MHPD materials was rough due to grafting. The results showed that the 1,5’-diphenylcarbazide treatment improved the removal efficiency of Cr(VI).

This thesis deals with the stopping of hydration of alkali activated slag by organic solvents and investigates to what extent the selected organic solvent affects the results of the analyses. The solvents used were acetone, diethyl ether, ethanol, isopropanol and methanol, and this is because these are the most commonly used organic solvents in practice. Thermogravimetric analysis along with differential thermal analysis was used to assess the degree of influence of organic solvents on the alkali activated slag and Portland cement samples. Methanol and acetone affected the samples the most and the longer the sample was stored in the solvent, the more it reacted with the organic solvent. The adverse interaction of organic solvent was greatest for the Portland cement samples. Samples that were rinsed with diethyl ether prior to analysis had lower mass losses than samples that were not rinsed. In the case of alkali activated slag, it was found that the way in which the thermogravimetric results were affected by organic solvents was highly dependent on the activator used, with the smallest effect observed for Na2CO3 activation, while the largest effect was observed for NaOH activation at temperatures below 600 °C, and for higher temperatures for water glass activation.

Tato práce se zabývá studiem termooxidační stability kompozitů polymethylmethakrylátu (PMMA) plněného mikro a nanočásticemi siliky. V připravených vzorcích byly použity různé objemové zlomky a různé velikosti částic siliky. Studium stability bylo prováděno pomocí termogravimetrie, která umožňuje simulovat podmínky termooxidační degradace. Indukční perioda byla stanovena za použití různých rychlostí ohřevu a aplikací izokonverzních metod. Závislosti teplot degradací na rychlostech ohřevu sloužily pro určení parametrů odvozených ze čtyř různých teplotních funkcí, které dovolují předpověď stability materiálu (indukční periody) při zvoleném rozsahu teplot. Zjištěné výsledky ukazují, že větší částice siliky snižuji stabilitu PMMA, zatímco nanočástice v nízkých koncentracích ji nijak neovlivňují.

Cancrinite specimens from Ontario were studied. Chemical and thermogravimetric analyses were made. Non-Bragg reflections were observed in x-ray photographs. These reflections have the same symmetry as the main lattice reflections, but the intensities, abundance and the relative positions of them with respect to the main lattice reflections are different from one specimen to another. In the heated specimens, the superstructure reflections decrease in intensities, shift in position and are streaked in a direction parallel to the a*-axis on the a* c* reciprocal lattice plane. Phase changes in the heated cancrinites show that the sodalite group of minerals occur as transitional phases in the cancrinite break down reactions. It is shown that the non-Bragg reflections are very similar to the main lattice reflections. There is a probable relation between the non-Bragg reflections in cancrinite and the sodalite group of minerals. / Thesis / Master of Science (MSc)

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