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Environmental pollution has been a serious concern worldwide. Many degradation methods have been developed to clean sites contaminated with pollutants. More knowledge and better understanding in this field will help to protect our environment. The goal of the research in this thesis is to gain a better understanding of the mechanism of organic pollutant degradation in Fenton reactions and sonochemical reactions. Fenton degradation uses hydroxyl radical to oxidize organic compounds. The radical is produced by catalytic decomposition of hydrogen peroxide with Fe(II). Further research has found that addition of cyclodextrins can enhance degradation efficiency of hydrophobic organic pollutants. To study the mechanism of the enhancement, pollutant-cyclodextrin-Fe(II) aqueous systems were studied by fluorescence and NMR techniques. The results indicated the formation of pollutant/carboxymethyl-â-cyclodextrin/Fe(II) ternary complexes in the solution. With the ternary complex, the catalyst Fe(II) becomes closer to the pollutant, therefore leading to more efficient hydroxyl radical attack on the pollutant. Additional studies showed that hydropropyl-â- cyclodextrin, â-cyclodextrin and á-cyclodextrin bound pollutant well, but bound Fe(II) poorly. Sulfated-â-cyclodextrin did not bind well with pollutant although it bound Fe(II) well. Sonochemical degradation is another important pollutant treatment method in practice. It was found that phenol sonolysis can be enhanced by volatile hydrogen atom scavengers such as carbon tetrachloride and perfluorohexane. The non-volatile hydrogen atom scavenger iodate did not enhance phenol degradation. The first order rate constant for aqueous phenol degradation increased by about 2.2-2.8 times in the presence of 150 ìM carbon tetrachloride. In the presence of less than 1.5 ìM perfluorohexane the first order rate constant increased by about 2.3 times. Hydroquinone was the major observed reaction intermediate both in the presence and absence of hydrogen atom scavengers. Hydroquinone yields were substantially higher in the presence of hydrogen atom scavengers, suggesting that hydroxyl radical pathways for phenol degradation were enhanced by the hydrogen atom scavengers. The additives investigated in this study have potential to improve pollutant degradation efficiency. Other fields may also benefit from the information gained in this study. For example the improvement could be achieved in synthetic processes that rely on hydroxyl radical as a key intermediate.

γ-Al2O3 supported Co-W based catalysts with varying Co (1 - 3 wt %) and W (7 - 13 wt %) loadings were prepared using impregnation and sonochemical methods. All prepared catalysts were characterized with elemental analysis, BET analysis, X-ray diffraction (XRD), NH3 temperature programmed desorption (TPD), temperature programmed reduction (TPR) and thermogravimetry analysis (TGA). <p>The performances of all the synthesized catalysts were tested at a pressure of 8.9 MPa, LHSV of 2 h-1 and temperatures of 340, 350 and 360 °C in a laboratory trickle bed microreactor for hydrodesulphurization (HDS) and hydrodenitrogenation (HDN) of light gas oil (LGO) derived from Athabasca bitumen. The performance tests with impregnated catalysts indicated a maximum in activity for HDS and HDN reactions (sulfur and nitrogen conversions at 93.0 and 57.1 % at 360 °C) for Co(3 wt %)-W(10 wt %)/γ-Al2O3 whereas the performance tests with sonochemically prepared catalysts showed a maximum in activity (sulfur and nitrogen conversions at 87.9 and 42.5 % at 360 °C) for Co(3 wt %)-W(11.5 wt %)/ γ-Al2O3. These two catalysts were selected for detail performance, optimization and kinetic studies. The effects of reaction temperature (340 - 380 °C), pressure (7.6 - 10.3 MPa), liquid hourly space velocity (1.5 - 2.0 h-1) and hydrogen gas/gas oil ratio (400 - 800 mL/mL) were examined on HDS and HDN of LGO with these catalysts. The reaction kinetics for HDS was best fitted with a Power Law model whereas same for HDN was found to be best represented by a Langmuir-Hinshelwood model with a reasonable accuracy (0.90 <R2 <0.95). The activation energy for HDS of LGO were 14 and 12 kJ/mol for selected impregnated and sonochemically prepared catalysts whereas the same for HDN were 9 and 14 kJ/mol for these catalysts, respectively. Calculation showed that the fitted HDS rate expressions were apparent and HDN rate expressions were intrinsic under existing reaction conditions. It also showed that the pore diffusion resistances for both HDS and HDN increased with an increase in reaction temperature from 340 to 380 °C.

γ-Al2O3 supported Co-W based catalysts with varying Co (1 - 3 wt %) and W (7 - 13 wt %) loadings were prepared using impregnation and sonochemical methods. All prepared catalysts were characterized with elemental analysis, BET analysis, X-ray diffraction (XRD), NH3 temperature programmed desorption (TPD), temperature programmed reduction (TPR) and thermogravimetry analysis (TGA). <p>The performances of all the synthesized catalysts were tested at a pressure of 8.9 MPa, LHSV of 2 h-1 and temperatures of 340, 350 and 360 °C in a laboratory trickle bed microreactor for hydrodesulphurization (HDS) and hydrodenitrogenation (HDN) of light gas oil (LGO) derived from Athabasca bitumen. The performance tests with impregnated catalysts indicated a maximum in activity for HDS and HDN reactions (sulfur and nitrogen conversions at 93.0 and 57.1 % at 360 °C) for Co(3 wt %)-W(10 wt %)/γ-Al2O3 whereas the performance tests with sonochemically prepared catalysts showed a maximum in activity (sulfur and nitrogen conversions at 87.9 and 42.5 % at 360 °C) for Co(3 wt %)-W(11.5 wt %)/ γ-Al2O3. These two catalysts were selected for detail performance, optimization and kinetic studies. The effects of reaction temperature (340 - 380 °C), pressure (7.6 - 10.3 MPa), liquid hourly space velocity (1.5 - 2.0 h-1) and hydrogen gas/gas oil ratio (400 - 800 mL/mL) were examined on HDS and HDN of LGO with these catalysts. The reaction kinetics for HDS was best fitted with a Power Law model whereas same for HDN was found to be best represented by a Langmuir-Hinshelwood model with a reasonable accuracy (0.90 <R2 <0.95). The activation energy for HDS of LGO were 14 and 12 kJ/mol for selected impregnated and sonochemically prepared catalysts whereas the same for HDN were 9 and 14 kJ/mol for these catalysts, respectively. Calculation showed that the fitted HDS rate expressions were apparent and HDN rate expressions were intrinsic under existing reaction conditions. It also showed that the pore diffusion resistances for both HDS and HDN increased with an increase in reaction temperature from 340 to 380 °C.

55 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-10-02T13:52:06Z No. of bitstreams: 1 Dissertação_Impressão FINAL.pdf: 23959288 bytes, checksum: 4ba5e564089149b8fafe9a4c74558367 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-10-02T14:12:03Z (GMT) No. of bitstreams: 1 Dissertação_Impressão FINAL.pdf: 23959288 bytes, checksum: 4ba5e564089149b8fafe9a4c74558367 (MD5) / Made available in DSpace on 2013-10-02T14:12:03Z (GMT). No. of bitstreams: 1 Dissertação_Impressão FINAL.pdf: 23959288 bytes, checksum: 4ba5e564089149b8fafe9a4c74558367 (MD5) Previous issue date: 2013 / O sulfeto de bismuto faz parte da família de compostos do tipo A2VB3VI formados por calcogênios e metais (sendo A= Sb, Bi. B= S, Se, Te) que se destacam por suas propriedades semicondutoras. O Bi2S3 forma um sólido de coloração preta de solubilidade muito baixa em água, possuindo energia de band gap na faixa de 1,3 a 1,7 eV, com potencial para aplicações nas áreas de optoeletrônica e fotocatálise, entre outras. As propriedades físicas e químicas de nanopartículas de Bi2S3, e outros nanomateriais, são fortemente dependentes de diferentes tamanhos e morfologias dos nancristais. Este trabalho teve como objetivo desenvolver um método sonoquímico para produção de nanopartículas de Bi2S3. Utilizou-se os reagentes Bi(NO3)3 e Na2S2O3 como precursores dissolvidos em solvente orgânico contendo o surfactante brometo de cetiltrimetilamônio (CTAB), sendo o meio reacional exposto a irradiação de ultrassom de alta intensidade, através de um sistema com sonda de titânio e imersão direta. As nanopartículas de Bi2S3 obtidas foram caracterizadas por difração de raios X (XRD), microscopia eletrônica de varredura (MEV) e microscopia eletrônica de transmissão (TEM). O método sonoquímico foi otimizado através do planejamento fatorial completo em dois níveis, onde se verificou que os parâmetros ciclo das ondas ultrassônicas e tempo influenciam significativamente no rendimento da reação. Fixando-se o ciclo em 80% e a amplitude em 20%, verificou-se que no tempo de reação de 15 min foram obtidas as nanopartículas com menor diâmetro médio (11,8 nm) e cristalinidade satisfatória. O método sonoquímico (15 min) foi comparado com o método de aquecimento convencional sob refluxo (90 min), mostrando-se mais rápido e eficiente na obtenção de nanopartículas com alta homogeneidade morfológica. O método sonoquímico produziu superestruturas tipo flor (3D) formadas pela agregação de nanobastões de Bi2S3 com diâmetro médio em torno de 11-15 nm. A morfologia e a qualidade dos nanocristais mostraram-se dependentes do tipo de solvente empregado na síntese. Superestruturas em 3D semelhantes a flores foram obtidas quando etilenoglicol puro foi usado como solvente, enquanto estruturas em 1D na forma de nanobastões foram obtidas quando se utilizou uma mistura de dimetilsulfóxido e etilenoglicol. Foi proposto um mecanismo para a síntese sonoquímica do Bi2S3 e os papéis do solvente e do surfactante nesta síntese foram discutido / Salvador

Made available in DSpace on 2014-06-11T19:30:19Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-05-05Bitstream added on 2014-06-13T18:40:20Z : No. of bitstreams: 1 arruda_lb_me_bauru.pdf: 4132261 bytes, checksum: ec76a96792be6b1907a354c279109181 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Há cerca de 20 anos foi descoberto o efeito magnetoresitivo em multicamadas magnéticas. Desde então, a spintrônica evoluiu de um fenômeno científico complexo para tornar-se uma tecnologia multibilionária. Dentre os parâmetros necessários para o desenvolvimento da spintrônica - a nova eletrônica que se baseia na manipulação não somente da carga, mas também do spin dos portadores -, está o controle eficiente da injeção e a detecção de portadores polarizados em spin, através de uma interface ferromagneto/semicondutor (isolante) - FM/SC(I). A utilização de semicondutores magnéticos diluídos (SMD), como ferromagnetos polarizadores de corrente, é uma solução possível para melhorar a eficiência na injeção de correntes de spins. A despeito do bom desempenho obtido com os SMDs funcionais desenvolvidos até hoje, sua baixa temperatura crítica impossibilita a utilização em temperatura ambiente. Atualmente, o progresso no campio da spintrônica depende fortemente do desenvolvimento de novos SMDs, nos quais as informações de carga e spin passam se manipuladas externamente em altas temperaturas. Em especial, é possível o desenvolvimento de semicondutores magnéticos diluídos que sejam transparentes, aumentando em muito seu potencial de aplicação em dispositivos magneto-ópticos, o que os torna naturalmente muito mais interessantes do que eletrodos ferromagneticos metálicos. A presente proposta se enquadra no plano de ampliação das linhas de atuação do grupo que inclui a implementação de técnicas sonoquímicas de síntese de materiais nanoestruturados, com potenciais aplicações em spintrônica. A mesma está baseada na preparação de amostras nanoscópicas de ZnO e TiO2 dopadas com Co²+, preparadas por irradiação ultrassônica e que terão sua estrutura investigada pelas técnicas de difração de Raios X (DRX) e microscopias eletrônicas (MEV e MET)... / The phenomenon of magnetoresistive effect was discovered about twenty years ago in magnetic multilayers and opened a new field in physics, the so called spintronics, which is based on the manipulation of not only charge but also the spin of the carriers. Also, the efficient control of injection and detection of spin polarized carriers through an interface ferromagnetic/semiconductor insulator plays a role. Since then, the field of spintronics-based devices changed from an only complex scientific problem to become a multibillionaire technological issue. The use of diluted magnetic semiconductors (DMS) as current polarizers ferromagnets is one possible solution to the improvement of efficiency in the injection of spin currents. Despiste the good performance obtained with the functional DMS, their low critical temperature makes impossible the use of such devices at room temperature. Currently, progress in the field of spintronics depends heavily on the development of new DMSs, in which the charge and spin information can be manipulated at higher temperatures. In particular, it is possible the development of diluted magnetic semiconductors that are transparent; highly increasing potential application of these materials in magneto-optical devices, making them more interesting than ferromagnetic metalic electrodes. This work fits into the expansion plan of action lines of our group that includes the implementation of sonochemical technics of nanostructured materials with potential applications in spintronics, based on the preparation of nanometric size samples of Co²+ - doped ZnO and TiO2. prepared by ultrasonic irradiation. Structural characterization was performed by X-ray diffraction analyses (XRD) associated to Rietveld Refinement and electronic microscopy techniques (SEM and TEM). The optical characterization was done by UV-Vis mesurements between 200 and 800 nm and evaluating... (Complete abstract click electronic access below)

Orientador: Paulo Noronha Lisboa Filho / Banca: Paulo Sergio Pizani / Banca: Americo Sheitiro Tabata / O programa de Pós graduação em Ciência e Tecnologia de Materiais, POSMAT, tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi da UNESP / Resumo: Há cerca de 20 anos foi descoberto o efeito magnetoresitivo em multicamadas magnéticas. Desde então, a spintrônica evoluiu de um fenômeno científico complexo para tornar-se uma tecnologia multibilionária. Dentre os parâmetros necessários para o desenvolvimento da spintrônica - a nova eletrônica que se baseia na manipulação não somente da carga, mas também do spin dos portadores -, está o controle eficiente da injeção e a detecção de portadores polarizados em spin, através de uma interface ferromagneto/semicondutor (isolante) - FM/SC(I). A utilização de semicondutores magnéticos diluídos (SMD), como ferromagnetos polarizadores de corrente, é uma solução possível para melhorar a eficiência na injeção de correntes de spins. A despeito do bom desempenho obtido com os SMDs funcionais desenvolvidos até hoje, sua baixa temperatura crítica impossibilita a utilização em temperatura ambiente. Atualmente, o progresso no campio da spintrônica depende fortemente do desenvolvimento de novos SMDs, nos quais as informações de carga e spin passam se manipuladas externamente em altas temperaturas. Em especial, é possível o desenvolvimento de semicondutores magnéticos diluídos que sejam transparentes, aumentando em muito seu potencial de aplicação em dispositivos magneto-ópticos, o que os torna naturalmente muito mais interessantes do que eletrodos ferromagneticos metálicos. A presente proposta se enquadra no plano de ampliação das linhas de atuação do grupo que inclui a implementação de técnicas sonoquímicas de síntese de materiais nanoestruturados, com potenciais aplicações em spintrônica. A mesma está baseada na preparação de amostras nanoscópicas de ZnO e TiO2 dopadas com Co²+, preparadas por irradiação ultrassônica e que terão sua estrutura investigada pelas técnicas de difração de Raios X (DRX) e microscopias eletrônicas (MEV e MET)... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The phenomenon of magnetoresistive effect was discovered about twenty years ago in magnetic multilayers and opened a new field in physics, the so called spintronics, which is based on the manipulation of not only charge but also the spin of the carriers. Also, the efficient control of injection and detection of spin polarized carriers through an interface ferromagnetic/semiconductor insulator plays a role. Since then, the field of spintronics-based devices changed from an only complex scientific problem to become a multibillionaire technological issue. The use of diluted magnetic semiconductors (DMS) as current polarizers ferromagnets is one possible solution to the improvement of efficiency in the injection of spin currents. Despiste the good performance obtained with the functional DMS, their low critical temperature makes impossible the use of such devices at room temperature. Currently, progress in the field of spintronics depends heavily on the development of new DMSs, in which the charge and spin information can be manipulated at higher temperatures. In particular, it is possible the development of diluted magnetic semiconductors that are transparent; highly increasing potential application of these materials in magneto-optical devices, making them more interesting than ferromagnetic metalic electrodes. This work fits into the expansion plan of action lines of our group that includes the implementation of sonochemical technics of nanostructured materials with potential applications in spintronics, based on the preparation of nanometric size samples of Co²+ - doped ZnO and TiO2. prepared by ultrasonic irradiation. Structural characterization was performed by X-ray diffraction analyses (XRD) associated to Rietveld Refinement and electronic microscopy techniques (SEM and TEM). The optical characterization was done by UV-Vis mesurements between 200 and 800 nm and evaluating... (Complete abstract click electronic access below) / Mestre

Submitted by Ana Carolina da Silva (aninha_010@hotmail.com) on 2018-07-03T00:00:59Z No. of bitstreams: 1 Dissertação_AnaCarolinaSilva.pdf: 2472051 bytes, checksum: 6b85b8c0d79a2746f5c893ab3a192b5e (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-07-03T12:37:12Z (GMT) No. of bitstreams: 1 silva_ac_me_bauru.pdf: 2472051 bytes, checksum: 6b85b8c0d79a2746f5c893ab3a192b5e (MD5) / Made available in DSpace on 2018-07-03T12:37:12Z (GMT). No. of bitstreams: 1 silva_ac_me_bauru.pdf: 2472051 bytes, checksum: 6b85b8c0d79a2746f5c893ab3a192b5e (MD5) Previous issue date: 2018-05-04 / Pesquisas científicas associadas à osseointegração promoveram grande avanço no tratamento para a reabilitação bucal com um prognóstico de sucesso superior a 90%. O fenômeno da osseointegração corresponde à conexão direta estrutural e funcional entre o tecido ósseo e o material do implante odontológico. O sucesso da osseointegração está associado primordialmente com a estabilidade primária durante o procedimento de instalação do implante e posteriormente com a estabilidade secundária após o procedimento. Altos índices de fracasso e perda de implantes têm sido atribuídos a implantes em osso de qualidade baixa e consequentemente com estabilidade diminuída, fato este recorrente em especial à pacientes com densidade mineral óssea (BMD) reduzida. Uma opção utilizada pela Implantologia é o uso materiais para enxerto ósseo, associado eventualmente à ingestão oral de fármacos que induzam a regeneração óssea. Os biovidros ativos são comumente utilizados como opção para enxertos, pois alegadamente promovem o crescimento ósseo. Dentre as opções de fármacos disponíveis no mercado farmacêutico, o Cloridato de Raloxifeno tem apresentado resultados satisfatórios quando comparado com a reposição hormonal à base de estrógeno ou ao uso de bifosfonatos de primeira geração. Este projeto tem como motivação o desenvolvimento de um material híbrido a base do biovidro ativo comercial BioGran® (enxerto ósseo) e o fármaco comercial Raloxifeno®, sintetizado pela técnica sonoquímica estudados os efeitos de indução ao crescimento ósseo do tempo de sonicação do biovidro e também de diferentes concentrações em massa do fármaco em relação à massa do biovidro. Os resultados mostraram que a variável tempo de sonicação não resultou em diferenças significativas da diminuição do tamanho das partículas do biovidro. Também, os resultados indicaram que o grupo com 20% em massa de raloxifeno apresentou os melhores resultados de regeneração óssea. / Scientific research associated to osseointegration promoted a great advance in the treatment for oral rehabilitation with a success prediction of over 90%. The phenomenon of osseointegration corresponds to the direct structural and functional connection between the bone tissue and the material of the dental implant, and a determinant concept in osseointegration is the primary stability, sought after the implant installation procedure. High failure rates and implant loss have been attributed to poor quality bone implants and consequently decreased primary stability, especially in patients with reduced bone mineral density (BMD). One of the options used in the filed of Implantology is the use of materials for bone grafting, associated with oral intake of drugs that induce bone regeneration. Active bio-biopsies are commonly used as an option for grafts because they allegedly promote bone growth. Among the drug options available in the pharmaceutical market, Raloxifene hydrochloride has shown satisfactory results when compared with estrogen-based hormone replacement or the use of first-generation bisphosphonates. This project has as a motivation in the development of a hybrid material based on BioGran® commercial active bioglass (bone graft) and the commercial drug Raloxifeno®, synthesized by the sonochemical technique studied the effects of induction to the bone growth of the sonication time of the bioglass and also of different concentrations of the drug in relation to the mass of the bioglass. The results showed that the sonication time variable did not result in significant differences in the decrease of the bioglass particle size. Also, the results indicated that the group with 20% in mass of raloxifene presented the best results of bone regeneration.

Active substances can be stabilized to be protected from undesirable reactions, aggregation, and leaking, which would keep the intended functions of the active substances without premature degradation. Among such active substances are paraffin-based organic phase change materials (PCMs) and essential oils (EOs), which feature attractive characteristics, e.g., high latent heat of fusion and inherent antimicrobial activity. However, their high volatility requires an effective stabilization strategy. Petroleum-based synthetic polymers have often been employed to stabilize PCMs and EOs by encapsulation and complexation pathways. Despite their proven effectiveness, these polymers are from non-renewable resources, and non-degradable and often toxic, which has prompted a need to develop a substitute arising from natural polymers that are environmentally benign, biodegradable, and sustainable. Valorization of biomass in this regard would add extra value to biomass otherwise burned or wasted. This dissertation will present the development of microcapsules and inclusion complexes consisting of a hydrophobic active substance core and a polysaccharidic shell originating from biomass. The first two chapters will explain the introduction and experimental details. Chapter 3 will present the microencapsulation of n-hexadecane as PCM via oil-in-water (O/W) Pickering emulsions stabilized by unmodified cellulose nanofibrils (CNFs) through a sonochemical technique. Chapter 4 will investigate the incorporation of the PCM-CNF microcapsules into TEMPO-oxidized CNF films for building application. Finally, Chapter 5 will show the synthesis of EOs-beta cyclodextrin (βCD) inclusion complexes as a guest-host system through a sonochemical technique.

Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: It was found that bacterial sludge from anaerobic water treatment systems is produced internationally at a rate of 60 grams per person per day and the accumulation of the potentially hazardous by-product has become of increasing concern. The produced bacterial sludge is frequently pumped into dams, dried out and used as agricultural fertilizer. This bacterial sludge is expected to have a relatively high heating value and as such, has the potential to produce energy from the biomass. It is, therefore, advisable to utilize this energy potential as an alternative to conventional sludge disposal. This project aimed to improve the yield of syngas by optimizing the reactor design to partially oxidize bacterial sludge using a sonochemical reactor that is operated at bulk atmospheric conditions. The effect of different conditions was investigated and the optimum settings for syngas production were found by investigating temperature, pressure and the effect of the amplitude of operation that regulates the energy input by the ultrasonic equipment. The optimum conditions were used to investigate the kinetics involved in this process as well as to determine the energy consumption by the process. It was also required to study the feasibility of partially oxidizing bacterial sludge using a sonochemical reactor instead of conventional steam gasification and also as an alternative means of sludge disposal. By eliminating this pollutant source, the future environmental threat posed by an increasing population size will be minimized and energy will be utilized from a thus-far wasted energy source. The syngas that is produced is used as a green alternative to fossil fuels in the Gas-to-Liquids (GTL) process to produce liquids fuels. A thus-far wasted energy source will be consumed and fossil fuels can be saved in the process. It was found that the maximum hydrogen mole percentage produced is 0.141 mole % of the vapour phase with the maximum carbon monoxide mole percentage in the vapour phase at 1.896 mole %. This shows an improvement on work conducted by Beyers (2011) of 59 % for hydrogen, 92% for carbon monoxide and a reduction of 49 % for carbon dioxide. A kinetic study of the process indicated that the rate equations that describe the hydrogen and carbon monoxide production are zero order and, therefore, independent of initial concentration of the sludge. The rate constants were 0.0146 (mol % hydrogen/s) and 0.0183 (mol % hydrogen/s) for hydrogen and carbon monoxide, respectively. It was found that the most severe change to the higher heating value of the feed was a mere 0.27 mJ/kg from an original value of 9.81 mJ/kg. This therefore confirms that the reaction has not proceeded to completion. The statistical model predicted a maximum value for hydrogen production at 0.151 mole % in the product gas, 0.01 mole % from the measured maximum. It was also found that hydrogen is produced during the sonolysis of distilled water and that this confirms that the hydrogen production during partial oxidation of the sludge sample comes mainly from the water present in the sludge. The hydrogen produced when only using water, was found to be 0.127 mole % and when using the active sludge, the value was 0.116 mole % hydrogen in the vapour phase. The thermal decomposition of calcium carbonate in the lime that is used to treat the pH of the unit where the sludge originates from, followed by the formation of carbon monoxide during the Boudouard reaction, led to an increased amount of carbon monoxide present in the product gas. Ultrasonic intensity is defined as the amount of energy that is transferred to the sample per cubic meter of the internal surface area of the reactor vessel. It was found that the intensity that was delivered to the reactant was lower than expected as the reactor was operating at an efficiency of only 36%. The design intensity was 1.44 W/m2 and the actual delivered intensity was 0.52 W/m2. Based on a maximum yield of 0.00012 Nm3/kg, the cost of syngas production under the conditions described by this study, would amount to R 19.98/Nm3. This cost only implicates the operational expenses and does not take further downstream processing and initial capital investment repayments into account. Conventional steam gasification at a yield of 0.67 Nm3/kg has an operational syngas production cost of R 1.48/Nm3. This process was therefore found to not be economically feasible as the cost of utilizing ultrasound as opposed to normal steam gasification is more than ten times more expensive. It was concluded that the process was successfully optimized by the redesigning of the reactor and that carbon dioxide production was limited by excluding oxygen from the feed gas. It was also concluded that the sonolysis of water and the thermal decomposition of calcium carbonate, followed by the conversion of carbon dioxide to carbon monoxide, supplements the syngas production under the current operational conditions. Based on the production of no methane during the course of this study, the sonochemical process can be tied into the GTL process after the steam reforming unit. Due to the relatively high carbon dioxide content, the process will need to join the main feed gas stream that is fed into the carbon dioxide removal unit before it enters the GTL process to correct the desired feed gas ratio. Based on the very low syngas yields, the low hydrogen to carbon monoxide ratio in comparison to the required ratio of 2 as well as the high energy intensity required for this process, it can be concluded that the partial oxidation of biomass sludge in a sonochemical reactor is not feasible as an alternative technology to conventional steam gasification. The operating costs of the sonochemical unit would be nearly ten times that of steam gasification and is therefore concluded to not be a competitive technology to conventional steam gasification. It is recommended that the reactor design is reinvestigated to improve the delivered ultrasound intensity as well as the surface area where the ultrasonic waves are intensified. This would eliminate dead-zones. It was also recommended that the argon gas is continuously bubbled through the reactant mixture during experiments to eliminate the degassing effect caused when the ultrasound is initially emitted. The gas outlet of the process can then be connected to an online gas chromatograph (GC) with a thermal conductivity detector (TCD) and flame ionization detector (FID) methanizer in series as the TCD does not destroy the sample and this setup would improve the analytical process. The production of carbon monoxide from lime as well as the production of hydrogen from water during sonolysis needs to be investigated. The effect of radicals can also be studied by the addition of a radical scavenger to the process. It is recommended that the experimental design is reinvestigated and a design that will deliver similar information utilizing fewer data points should be chosen. Based on this model as well as further kinetic testing, it is recommended that a complete ASPEN model is developed to simulate the energy requirements to tie the ultrasonic process into the commercial plant. Based on this model, a complete feasibility study can then be conducted to determine the capital costs involved, the operating costs, the repayment period as well as taking the current costs of sludge disposal into account. / AFRIKAANSE OPSOMMING: Daar is gevind dat bakteriele slik internasionaal geproduseer word deur anaerobiese waterbehandelingseenhede teen ‘n tempo van 60 gram per person per dag en dat die opberging van hierdie gevaarlike byproduk ‘n groeiende probleem word. Die geproduseerde bakteriele slik word in damme gestoor, uitgedroog of gebruik as kunsmis in die landbou bedryf. Daar word vermoed dat hierdie baketriele slik oor ‘n hoe verwarmings waarde beskik en het daarom die potensiaal om energie te produseer uit die biomassa. Daarom is dit voorgestel om alternatiewe prosesse te ondersoek om van hierdie slik ontslae te raak en moontlik die energie wat beskikbaar is te gebruik. Die projek is daarop gefokus om die produksie van syngas te verbeter deur die reaktorontwerp te optimeer deur gebruik te maak van parsiele oksidasie van slik onder atmosferiese kondisies deur klankgolwe te gebruik. Die effek van verskillende operasionele kondisies is ondersoek en die optimale vlakke van syngas produksie is gevind deur temperatuur, druk en amplitude wat die hoeveelheid energie wat oorgedra word aan die reaktor reguleer, te ondersoek. Die optimale kondisies is ook gebruik om die kinetiese aspekte van die proses te ondersoek en ook om te kyk wat die sisteem se energie benodighede behels. Die haalbaarheid om baketriele slik parsieel te oksideer in ‘n sonochemiese reaktor is vergelyk met dit van konvensionele stoom vergassing van die biomassa en is ook ondersoek as ‘n alternatief om van die slik ontslae te raak. Deur die slik te verwyder as ‘n potensiele bron van besoedeling, kan die toekomstige omgewing’s risiko wat deur die toename in die bevolkkingsgroote tot gevolg is, verwyder word deur ‘n energie bron te gebruik wat tot dusver geignoreer is. Die syngas wat geproduseer word kan dan gebruik word in die “Gas-to-Liquids” (GTL) process om vloeistof brandstowwe te produseer. Dus sal ‘n omgewingsrisiko verminder word, ‘n energiebron word benuttig wat nooit van tevore benuttig is nie en fosiel brandstowwe kan gespaar word. Die maksimum waterstof wat geproduseer is, was 0.141 mol % in die gas fase met ‘n maksimum waarde vir koosltof monoksied van 1.896 mol % in die gas fase. Dit toon ‘n verbetering van 59 % vir waterstof, 92 % vir koolstof monoksied en ‘n vermindering van 49% in die koolstof dioksied wat deur Beyers (2011) geproduseer is. Die kinetiese studie het ondervind dat die “rate equation” van waterstof en koolstofmonoksied beskryf word deur nul-orde kinetika. Hierdie konstantes was 0.0146 (mol % waterstof/s) en 0.0183 (mol % waterstof/s) vir waterstof en koolstofmonoksied. Daar is ook gevind dat die grootste moontlik verandering in die hoe verwarmings waarde van die biomassa is ‘n skamele 0.27 mJ/kg van die oorspronklike waarde van 9.81 mJ/kg. Hierdie waarneming staaf dus die uitkoms dat die reaksie dus nie tot die einde verloop het nie. Die statistiese model het ‘n maksimum van 0.151 mol % voorspel wat 0.01 mol % meer was as die waarde wat gemeet is. Dit is ook gevind dat waterstof geproduseer word deur die sonoliese van water en dat hierdie bykomende waterstof deel uitmaak van die produkgas aangesien die slik grootliks uit water bestaan.Die hoveelheid waterstof in die gas fase wat geproduseer is tydens sonoliese van ‘n suiwer water monster, was 0.127 mol %. Die hoeveelheid waterstof in die gas fase wanneer die slik behandel is ten optimal kondisies, was 0.116 mol % gemiddeld. Die hitte degradering van kalsium karbonaat wat teenwoordig is in die kalk wat gebruik word om die pH van die produksie eenheid te reguleer, gevolg deur die Boudouard reaksie, het tot gevolg dat addisionele koolstof monoksied ook gevorm word. Ultrasoniese intensiteit kan gedefineer word as die hoeveelheid energy wat oorgedra word aan ‘n reaktant gebasseer op die oppervlak area aan die binnekant van die reaktor. Die intensiteit waarteen die voermateriaal blootgestel word aan die klankgolwe was laer as verwag met ‘n 36 % effektiwiteit. Die ontwerp spesifiseer ‘n intensiteit van 1.44 W/m2 en die intensiteit wat fisies gelewer is, was 0.521 W/m2. Die maksimum produksie van syngas was 0.00012 Nm3/kg, wat lei tot ‘n operasionele koste van R 19.98/Nm3 onder die kondisies van hierdie studie. Hierdie koste neem nie die oorsponkilke kapitaal vir die konstruksie, of die koste van verdere behandelik van die gas, in ag nie. Konvensionele stoom vergassing teen ‘n opbrengs van 0.67 Nm3/kg het ‘n operasionele koste van R 1.48/Nm3 tot gevolg. Die proses is dus ekonomies nie ‘n aantreklike opsie nie aangesien die kostes van syngas produksie met ultraklank meer as tien keer meer is as konvensionele stoom vergassing. Daar is tot die gevolgtrekking gekom dat die reaktor optimering suksesvol was en deur geen stuurstof te voer nie, die koolstofdioksied persentasie verminder is. Daar is ook tot die gevolgtrekking gekom dat die sonoliese van water, en die hitte degradering van kalsium karbonaat, gevolg deur die Boudouard reaksie, die syngas produksie supplementeer. Aangesien geen metaan gedurende hierdie studie geproduseer is nie, kan die sonochemiese proses inskakel by die GTL aanleg na die stoom hervormingseenhed. As gevolg van die hoe koolstofdioksied konsentrasie, sal die prosesstroom gemeng moet word met die produk stroom uit die stoom hervormings proses, wat gevoer word na die koolstofdioksied verwyderings eenheid. Hierdie eenheid is daarvoor verantwoordelik om die korrekte verhouding van gasse vir die GTL voer stroom te reguleer. Gebasseer op die baie lae syngas opbrengs, die lae waterstof tot koolstofmonoksied verhouding en die hoe energie behoeftes, is daar tot die gevolgtrekking gekom dat die parsiele oksidasdie van die biomassa in ‘n sonochemiese reaktor nie ‘n haalbare alternatief is vir konvensionele stoom vergassing nie. Die operasionele koste van die sonochemiese eenheid is ongeveer tien keer meer as die van stoom vergassing en daarom is die proses nie kompeterend nie. Daar word voorgestel dat die reaktor ontwerp hersien word om die gelewerde intensiteit te verbeter, sowel as om die kontak area waar die klankgolwe gekonsentreer is, te vergroot. Dit sal dooie sones uitskakel. Daar word ook voorgestel dat argon gas gedurende die eksperiment aanhoudende geborrel word deur die reaktant vloeistof in die reaktor om die ontgassingseffek uit te skakel sodra die klankgolwe aangeskakel word. Die gas uitlaat kan dan inlyn gekoppel word aan ‘n gas chromatograaf met ‘n termiese geleidings detektor (TCD) en ‘n vlam ionisasie detektor (FID) met metaan omskakeling, aangesien die TCD nie die monster vernietig nie. Hierdie opstelling behoort analitiese methodes te verbeter. Die produksie van koolstofmonoksied uit kalk sowel as die produksie van waterstof uit water gedurende sonoliese, moet verder ondersoek word. Die effek van radikale kan ook verder bestudeer word deur die gebruik van ‘n radikaal rower gedurende die proses. Daar word ook voorgestel dat die statistiese ontwerp herondersoek word sodat minder eksperimente gebruik kan word om soortgelyke resultate te bekom met minder data punte. Gebasseer op hierdie nuwe model en ‘n kinetiese studie, word dit aangeraai dat ‘n volledige ASPEN model gebou word om te simuleer hoe hierdie sonochemiese eenheid sal inskakel met die kommersiele eenheid. Dit sal dan moontlik wees om die energie benodighede van die proses te verstaan en gebasseer daarop, kan ‘n volledige haalbaarheid studie gedoen word wat kyk na oorspronklike installasie kostes, onderhouskostes, operasionele kostes sowel as die terugbetaling van die konstruksie kostes. Dan kan ‘n vergelyking getref word met die huidige kostes om van hierdie slik ontslae te raak en om die slik as ‘n brandstof te benut.