A continuous process for the production of ceramic materials has been studied. This method reacted metal and oxidizer in a diffusionally controlled process, demonstrated by reacting a magnesium particle stream and hot water vapor. Many small rich hydrogen/air diffusion flames provide an atmosphere of hot water vapor, hydrogen, and nitrogen for oxidizing the magnesium, which reacts with the water vapor in the form of a diffusion flame. The burner that provides the hot atmosphere has been characterized thermally using thermocouple measurements and a model that gives the true temperature from the measured values. A model was developed that gives the flame profile for the parallel flow geometry of particle stream combustion used in this study as defined in the cartesian coordinate system. / Graduation date: 1995

This thesis is concerned with the design of a decoupling compensator and a time-delay compensator for a nonisothermal continuous flow stirred tank reactor (CFSTR). An expression for the analysis of interaction of the two-variable CFSTR was theoretically derived by using the relative gain method (RGM). For the purpose of improving the stability of the decoupling control system, undercompensation for a decoupled CFSTR system was suggested and the robustness test of such undercompensation decoupler to the modelling error was studied. On the other hand, the proposed time-delay compensation method, unlike conventional Smith's scheme, can rely on the basic property of gain-invariant time-delay. The stability of this time-delay compensation method is not affected by the CFSTR control system time-variant time-delay, while its compensation structure has the same features as the Smith compensator. The design of a decoupler and that of a time-delay compensator are independent of each other. All compensation structures are physically realizable. The theoretical results are supported by simulation. Simulation results for a CFSTR demonstrate that the undercompensation decoupling control can tolerate a relatively wide modelling error and reduce the sensitivity of the CFSTR process to parameter variations and unwanted disturbances. Also, simulation results show that the proposed time-delay compensator can provide an improvement over the conventional Smith compensator. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Thesis (PhD)--Stellenbosch University, 2001. / ENGLISH ABSTRACT: The photo-mineralization of organic compounds (in the combined presence of a Ti02 based semiconductor catalyst, UV radiation and molecular oxygen) represents an advanced oxidation technology with significant potential for environmental pollution abatement. This oxidation process (generally known as photocatalytic oxidation - PCO) is currently the subject of extensive global research, with the main objective being the oxidative removal of organic and inorganic pollutants from water, air and soil. Presently, many barriers still block the way to commercial implementation of this technology, hence a unique (and effective) configuration of catalyst, light source and reactor design needs to identified. In terms of the water treatment scenario (which is the emphasis of this work) the need exists to develop a practical and affordable PCO reactor for water treatment on a large scale. The two laboratory-scale PCO reactors investigated in this work were based on a "falling film" flow reactor design and were constructed with commercially available materials and components. Degussa P-25 Ti02 was used as semiconductor catalyst and two types of low-pressure mercury lamps as the UV light source. Three modes of operation were investigated in order to determine the practical feasibility of the reactors. These included the recirculation, single pass and sequential single pass modes. The reactors were operated either as a Ti02 slurry-phase reactor (Reactor 1), or with Ti02 immobilized on stationary fiber glass and fibrous activated carbon sheet modules (Reactors 2A and 28 respectively). Extensive parametric evaluations were done using conventional one-factor variation and statistical methods according to optimal experimental design principles. The PCO treatment of two model organic pollutants (para-Chlorophenol and cyanobacterial microcystin YA, YR, LR and RR) were investigated. These pollutants were spiked into various water matrices to the desired concentration level. The combined photocatalyticcarbon adsorption treatment of these two pollutants was also investigated in Reactor 28. The experimental results obtained through this work showed that both model pollutants were successfully degraded in several water matrices by means of treatment in the respective PCO reactors. Moreover, this research was the first ever demonstration of the Ti02 photocatalytic degradation of microcystin toxins in the aqueous phase. The large number of parametric and optimization studies yielded the relative contributions of the various process parameters (in terms of the defined photocatalytic efficiency parameters as responses) very effectively. Furthermore, statistical evaluation of the experimental data provided valuable insight into the scientific phenomena associated with Ti02 mediated PCO processes. / AFRIKAANSE OPSOMMING: Die foto-mineralisasie van organiese verbindings (in die gekombineerde teenwoordigheid van 'n Ti02 gebaseerde halfgeleier katalisator, UV straling en molekulêre suurstof) verteenwoordig 'n gevorderde oksidasie-tegnologie met beduidende potensiaal vir bekamping van omgewingsbesoedeling. Hierdie oksidasie-proses (algemeen bekend as fotokatalitiese oksidasie - FKO) is tans wêreldwyd die onderwerp van ekstensiewe navorsing, met hoofdoel die oksidatiewe verwydering van organiese en anorganiese besoedelingstowwe uit water, lug en grond. Huidiglik bestaan daar nog vele struikelblokke wat die weg na kommersiële implementering van hierdie tegnologie blokkeer, gevolglik moet 'n unieke (en effektiewe) konfigurasie van katalisator, ligbron en reaktor-ontwerp nog identifiseer word. In terme van die waterbehandeling situasie (wat die klem van hierdie werk is) bestaan die nodigheid om 'n praktiese en bekostigbare FKO reaktor te ontwikkel vir watersuiwering op 'n groot skaal. Die twee laboratorium-skaal FKO reaktore in hierdie studie was gebaseer op 'n "vallende film" vloeireaktor ontwerp en is gekonstrueer met kommersieël beskikbare materiale en komponente. Degussa P-25 Ti02 is aangewend as halfgeleier katalisator en twee tipes lae-druk kwik lampe as die UV ligbron. Drie bedryfsmodes is ondersoek met die doel om die praktiese haalbaarheid van die reaktore te bepaal. Hierdie het ingesluit die resirkulasie, enkeldeurvloei en enkeldeurvloei-sekwensie modes. Die reaktore is bedryf as óf 'n Ti02 flodder-fase reaktor (Reaktor 1) óf met Ti02 ge-immobiliseer op 'n stasionêre veselglas en veselagtige ge-aktiveerde koolstof blad-modules (Reaktor 2A en 28 onderskeidelik). Omvattende parametriese evaluasies is gedoen deur gebruik te maak van konvensionele een-faktor variasie en statistiese metodes na aanleiding van optimale eksperimentele ontwerp beginsels. Die FKO behandeling van twee modelorganiese besoedelingstowwe (para-Chlorofenol en siano-bakteriese mikrosistien YA, YR, LR en RR) is ondersoek. Hierdie besoedelingstowwe is ge-ent in verskeie watermatrikse tot die verlangde konsentrasievlak. Die gekombineerde fotokatalitiese - aktiveerde koolstof behandeling van die twee besoedelingstowwe is ook ondersoek in Reaktor 28. Die eksperimentele resultate verkry deur hierdie werk het getoon dat beide die modelbesoedelingstowwe suksesvol gedegradeer is in verskeie watermatrikse deur behandeling in die onderskeie FKO reaktore. Trouens, hierdie navorsing was die eerste demonstrasie ooit van die Ti02 fotokatalitiese degradasie van mikrosistien toksiene in die waterige fase. Die groot aantal parametriese en optimiseringstudies het die bydraes van die verskeie proses-parameters (in terme van die gedefinieerde fotokatalitiese effektiwiteitsparameters as response) baie effektief verskaf. Verder, statistiese evaluasie van die eksperimentele data het waardevolle insig verskaf tot die wetenskaplike verskynsels te assosieer met Ti02 gemedieërde FKO prosesse.

This dissertation presents a method for enhancement of the efficiency and scalability of photocatalytic water purification systems, along with an experimental validation of the concept. A 3-dimensional photocatalyst structure, made from a TiO2-SiO2 composite, has been designed and fabricated for use in a custom designed LED-source illumination chamber of rotational symmetry that corresponds with the symmetry of the photocatalyst material. The design of the photocatalyst material has two defining characteristics: geometrical form and material composition. The design of the material was developed through the creation of a theoretical model for consideration of the system's photonic efficiency. Fabrication of the material was accomplished using a Ti alkoxide solution to coat a novel 3D support structure. The coatings were then heat treated to form a semiconducting thin-film. The resulting films were evaluated by SEM, TEM, UV-vis spectroscopy and Raman spectroscopy. The surface of the material was then modified by implantation of TiO2 and SiO2 nanoparticles in order to increase catalytic surface area and improve the photoactivity of the material, resulting in increased degradation performance by more than 500%. Finally, the efficiency of the photocatalytic reactor was considered with respect to energy usage as defined by the Electrical Energy per Order (EEO) characterization model. The effects of catalyst surface modification and UV-illumination intensity on the EEO value were measured and analyzed. The result of the modifications was an 81.9% reduction in energy usage. The lowest EEO achieved was 54 kWh per cubic meter of water for each order of magnitude reduction in pollutant concentration -- an improvement in EEO over previously reported thin-film based photoreactors.

Lignin, the second most abundant biopolymer on earth following cellulose, can be described as a million-ton, low cost, under-utilized resource. The use of lignin in polymeric products adds the highest value to the raw material. Production of engineering plastics from lignin is an attractive approach to the utilization of lignin. The use of lignin in structural materials is limited by its insolubility and its failure to undergo melt flow. A promising method to overcome the limitations is to chemically modify lignin by reaction with a low modulus substance, like an aliphatic ether. The reaction of lignin with propylene oxide (PO) produces a copolymer, hydroxypropyl lignin (HPL). Extensive studies have been directed toward the understanding of the chemistry and properties of HPL. A study of the process design is necessary to examine the economics of lignin propoxylation. This work includes the chemical and kinetic analysis of the lignin propoxylation reaction as well as the modelling of a semibatch polymerization process; the design of a lignin propoxylation pilot plant; and a preliminary study of an industrial plant. Two models for the lignin propoxylation reaction are proposed and analyzed to produce a mathematical description of the reaction process. The design of the pilot plant involves (a) the process design, which includes a material balance, a flow sheet, and a listing of the equipment; and (b) the economic analysis in which estimates of capital cost and operating costs are discussed. The scale-up to industrial production gives an estimate of the characteristics of a continuous process. This study constitutes a substantial contribution to the development of a new technology dealing with Engineering Plastics from Lignin. / Master of Science

Orientador: Jose Roberto Nunhez / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-24T18:12:52Z (GMT). No. of bitstreams: 1 Peixoto_SimoneMariaCoimbra_M.pdf: 5964146 bytes, checksum: 8d9dc83b59e8adc5ad07e53b88e1c684 (MD5) Previous issue date: 1998 / Resumo: Os tanques de mistura são muito utilizados nas indústrias químicas para processar produtos de alto valor agregado. No entanto, apesar da sua grande importância nas indústrias químicas, poucas informações estão disponíveis sobre como o desempenho desses equipamentos é influenciado pela configuração mecânica do agitador, pelo tipo de superfície de troca térmica e pelo modo de operação. Um entendimento mais profundo destes fenômenos pode proporcionar meios de se otimizar projetos de reatores que sejam condizentes com uma melhor circulação interna do fluido e uma troca de calor mais eficiente. Este estudo tem o objetivo de estudar o arranjo geométrico de um tanque de mistura com um agitador tipo turbina Rushton e com serpentinas helicoidais para resfriamento conforme o trabalho sugerido por Oldshue e Gretton (1954), visto que até hoje este arranjo é utilizado por muitas indústrias nos projetos desses tanques. Trabalhos anteriores criticaram esta geometria porque este arranjo apresenta serpentinas posicionadas na altura da descarga do fluxo proveniente do agitador. Com as simulações realizadas neste estudo constatou-se que o arranjo do tanque com serpentinas pode sofrer modificações quanto à forma do tanque e ao arranjo do feixe de serpentinas, possibilitando a proposição de geometrias que proporcionam melhor mistura e controle de temperatura. Este trabalho utiliza o pacote computacional CFX-F3D para a realização das simulações. O modelo é bidimensional e o tanque opera em regime laminar. O pacote utiliza o método dos volumes finitos com variáveis colocalizadas e sistema de coordenadas "body-fitted" para resolver as equações do modelo. A comparação dos resultados obtidos, através de várias simulações de arranjos de serpentinas, permitiu a obtenção de um arranjo otimizado de serpentinas que apresenta um controle de temperatura mais eficiente e um melhor coeficiente de transferência de calor com minirnização dos gastos de energia / Abstract: Stirred tank reactors are extensively used in chemical industries to process low volume products of high value. Despite its importance, little is known about the performance of such systems. The mechanical configuration of the internals, in particular the impeller and the heat transfer surfaces, as well as mode of operation, have a deep effect in the flow. A deeper knowledge of the behaviour of such systems may provide ways to improve the mechanical designoThe aim of this study is to analyse the experimentalgeometry of a stirred tank reactor with a Rushton turbine impeller and helical coils according to the work of Oldshue and Gretton (1954), since this kind of configuration is still employed in reactor design in our days. Previous work criticised the experimental apparattus because it employs coils at the same height of the impeller blades. The simulated results showed that it is possible to modify vessel shape and coil helix which lead to designs consistent with better mixing and heat transfer. This work uses the CFX 4.1 fluid dynamics package for the calculations. The model calculates the three velocities in a two dimensional mesh for laminar flow. The software uses fínite volumes with colocalized variables and body fitted coordinates. Simulation results with varying vessel shapes and coil positions led to the determination of optimized designs with more efficient temperature control and better heat transfer coefficient, which allows reduced energy operating costs / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química