A cinza da casca do arroz (CCA) é um resíduo rico em sílica amorfa. Um método simples e de baixo consumo energético para extração desta sílica foi pesquisado, obtendo-se um material com baixo teor de impurezas e alta reatividade, adequado para a síntese de zeólitas e wolastonita (CaSiO3). As zeólitas sintéticas, que não possuem estruturas similares na natureza, são cada vez mais valorizadas no mercado devido a pureza e eficiência em aplicações específicas nas áreas de troca iônica, peneira molecular e catálise. A wolastonita com elevado grau de pureza tem várias aplicações na indústria e agricultura. O mineral wolastonita pode ser formado de várias maneiras na natureza. Em geral é aceito que existem dois processos de formação; os quais envolvem o metamorfismo (calor e pressão) do calcário. Neste trabalho, foi desenvolvido um novo processo para a síntese das zeólitas e da wolastonita, ambas a partir da sílica coloidal da CCA; tendo como objetivo um processo de um menor custo energético, menor número de etapas e menor consumo de reagentes. Foram sintetizadas neste trabalho as zeólitas: A, usada em detergentes, e a ZSM-5, empregada na indústria petroquímica, devido a sua alta seletividade em reações catalíticas e grande estabilidade térmica e resistência aos ácidos. A primeira etapa na síntese da wolastonita foi estudada com o objetivo da formação do hidrossilicato de cálcio (CSH). Contudo, onze hidrossilicatos de cálcio diferentes ocorrem no sistema Ca(OH)2-SiO2-H2O que em uma segunda etapa passam por um tratamento térmico para dar formação a fase wolastonita. / Rice hull ash (RHA) is a industry scrap rich in amorphous silica. A simple and low-energy cost method for the extraction of this silica was researched. A low level of impurity and high reactivity material was produced, which is appropriate for the synthesis of zeolites and wolastonite (CaSiO3). The synthetic zeolites, has not similar structures in nature, and they have been more and more valued in the market due to their purity and efficiency in specific applications like ion exchange, molecular sieve and catalysis areas. High purity wolastonite has many applications in manufacturing and agriculture. The mineral wolastonite can be formed in nature in different ways; it is generally accepted two forming processes, both encompassing limestone metamorphism (heat and pressure). In this work, a new process for the synthesis of zeolites and wolastonite from RHA colloidal silica was developed. Moreover, the process is aimed at lower energy costs, fewer stages and fewer reactants consume. In this work, zeolite A used in detergent and zeolite ZSM-5, employed in the petrochemical industry due to its high selectivity in catalytic reactions and its high thermo and acid stability, were synthesized. The first step of the wolastonite synthesis was studied, with the purpose of obtaining calcium hydrosilicate. Eleven different hydrosilicates occur in the system Ca(OH)2-SiO2-H2O, in the second step, it was annealed to form the wolastonite phase.

Thesis (M.Sc.(Chemistry)) -- University of Limpopo, 2018. / Refer to the document / NRF-Sasol Inzalo Foundation

Recently, there has been growing interest in the green synthesis of zeolite (aluminosilicate) materials using solvent-free synthesis methods. Solid starting materials are typically ground for a period of time followed by thermal heating to synthesize crystalline ZSM-5 zeolite. These studies generally have focused on products formed after the thermal heating. However, very little is known about the reaction intermediates formed during the mechanochemical pre-reaction grinding step and how the pre-reaction impacts the subsequent synthetic success. In this study, the mechanochemical approach used to synthesize ZSM-5 and mordenite zeolite was investigated. Two types of solvent-free synthesis methods were investigated; templated solvent-free synthesis, and template-free and solvent-free synthesis. The effect of grinding time was investigated first to find the optimal grinding time that initiates pre-reactions between the starting materials. Controlled experiments were used to monitor chemical and physical changes occuring during the grinding step. Subsequently, the effect of different synthesis conditions such as time, temperature, template, SiO2/Al2O3, and Na2O/Al2O3 ratios, and different precursors were studied using the optimal grinding time. Both manual (mortar and pestle) and ball mill (FTS 1000) grinding were used in this study. The synthesized products were characterized using XRD, BET nitrogen adsorption, SEM, and ICP-OES. Finally, selected single-phase synthesized zeolite materials were evaluated for their catalytic performance in biomass conversion process of cellulose and glucose to useful chemicals such as hydroxymethylfurfural (HMF).

Graduation date: 1997

Biogas is a source of renewable energy and is produced at anaerobic conditions. The gas consists mainly of methane (55-70 %) and carbon dioxide (30-45 %). Biogas can be used as vehicle fuel after the gas has been upgraded to a methane content of approximately 97 %. There are several companies in Sweden producing biogas. Svensk biogas AB in Linköping is one of the largest. The company has two biogas production plants; one in Linköping and one in Norrköping. To meet the surge demand for biogas it is not only important to increase the volumetric capacity of the digesters, but also to optimize the process at the existing production plants in different ways. Zeolites, a clay mineral, have earlier been shown to have a positive effect on anaerobic digestion of certain substrates. The aim of this master’s thesis was to investigate if the organic loading rate could be increased and/or if the hydraulic retention time could be reduced by addition of zeolites to a reactor treating slaughterhouse waste as a substrate. The aim was further to investigate which substance/substances that zeolites possibly could affect. Addition of the zeolite clinoptilolite in a continuously stirred lab tank reactor showed a significantly lower accumulation of volatile fatty acids compared to that in a control reactor without zeolites added, when the hydraulic retention time was kept low (30 days) and the organic loading rate was high (4.8 kg VS/ (m3 × day)). The same results were observed upon zeolite addition in a batch experiment, which also showed a decreased lag phase. Neither the specific gas production nor the methane concentration was significantly affected by addition of zeolites. Furthermore, addition of a possible inhibitor, long-chain fatty acids (LCFA), increased the lag phase further when slaughterhouse waste was used as a substrate. The conclusion from the observed results is that a metabolite or metabolites produced during the anaerobic degradation is/are the reason to inhibition and an increased lag phase.

The equilibria of adsorption on calcium and hydrogen forms of zeolite Y by equimolar solutions of 12.5 %, 20%, 25%, 30% and 35% w/v of mixtures of glucose, G and fructose, F / also the non-equimolar mixtures of 20% w/v glucose - 30% w/v fructose, 30% w/v glucose - 20% w/v fructose, 25% w/v glucose &ndash / 35% w/v fructose, and 35% w/v glucose-25% w/v fructose solutions, which were prepared 24 hours in advance at the experimental temperature, have been studied batch wise at 50&ordm / C. Glucose adsorption, in solutions that had adsorption differences, was fast on both zeolites, on the contrary of slow adsorption of fructose with the stable dynamics. Both adsorptions had small amounts of adsorption changes after minute 30. The treatments made under the same conditions with the same mixtures showed Ca-Y zeolite had better separation capacity compared to H-Y zeolite. Some trials were repeated with CaCl2 added to the solutions. The slowed down affection of fructose adsorption in spite of the small change of glucose adsorption led to better separation. Samples were analyzed by classical methods, not HPLC. All the data were considered with various models and their convergence numbers were tested for their closeness to reality. The models were analyzed by response surface methodology and some of those models had correlation factors as high as 88% at the equilibrium points at 30th minutes. Besides, time dependent models have been considering the lag times with a time dependent variable included all the data of all treated solutions with correlation as high as 79.5%.

Thesis (M.S.)--Worcester Polytechnic Institute. / Keywords: Molecular dynamics; hydrophobic zeolite; water; confined media. Includes bibliographical references (p. 71).

M. Tech. Chemical Engineering. / Evaluates the use of modified eccalite as an adsorbent for the efficient removal of vanadium from industrial wastewater. The specific objectives of the study are: i. To determine whether modification of eccalite with a surfactant such as (hexadecyltrimethylammonium bromide HDTMA-Br, CTAB) will gives an optimal performance in vanadium removal from industrial wastewater; ii. To conduct batch adsorption experiments for modified eccalite for the determination of equilibrium adsorption capacity, kinetics, and thermodynamic parameters; iii. To perform column/dynamic adsorption experiments for modified eccalite in order to determine the dynamic adsorption capacity and breakthrough profiles. iv. Fit the experimental data to existing mathematical model describing the sorption process of vanadium removal from wastewater.

Electron crystallography has evolved as a powerful method for structural characterization of a wide range of materials. It has two significant advantages over other methods for structure determination, e.g. X-ray diffraction. Electrons interact much more strongly with matter compared to X-rays and they can be focused by electromagnetic lenses to form images with atomic resolution. These advantages make electron crystallography a unique tool for characterization of crystalline materials suffering from small crystal size and complex or disordered structures.      Zeolites are a class of microporous materials with significance in several applications. They often possess complex and disordered structures, which demand large efforts in the structure determination.      Over the last years, two new electron crystallographic methods have been developed; the rotation electron diffraction (RED) and the structure projection reconstruction from a through-focus series of high resolution transmission electron microscopy (HRTEM) images. In this thesis, they will be applied for structure determination of four new zeolite structures, including EMM-25 and EMM-23 with two ordered structures, and ITQ-39 and ITQ-38 with disordered structures. Each of the structure solutions have different challenges to overcome. The high silica borosilicate EMM-25 was solved by the RED method. The aluminosilicate EMM-23 was solved by a combination of HRTEM and RED. The structure solution of two materials with disordered structures, ITQ-39 and ITQ-38, will be described. For materials containing disorders, structure projection images are of utmost importance.      Furthermore, the mesoporosity inside hierarchically porous ZSM-5 crystals was studied by a combination of focused ion beam (FIB) and HRTEM imaging. The last part of this thesis explores STEM imaging for use in structure determination from 3D reconstruction. / <p>At the time of the doctoral defence the following papers were unpublished and had a status as follows: Papers 4 and 5: Manuscipts; Paper 10: Manuscript</p>

The conversion of switchgrass lignin, a renewable source for chemicals and fuels, is investigated using reactions such as depolymerization, hydrodeoxygenation and alkylation. First, the lignin is converted into oils containing phenol, substituted guaiacols and other smaller lignin fragments using formic acid and Pt/C through a batch process. A long reaction time was observed to crucial to yield oils with the highest fraction of lower molecular weight compounds with the lowest O/C and highest H/C molar ratio. Second, the zeolite catalyzed gas phase alkylation of phenol, a model compound for the lignin oil, with propylene was investigated. Zeolite pore topology and acid strength were shown to influence the selectivity for the target product, 2-isopropylphenol. This work shows that the conversion of lignin to useful products is possible and suggests some future work to consider before it can be implemented practically.