Abstract embargoed until 2030-11-11

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22428号 / 工博第4689号 / 新制||工||1732(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 酒井 伸一, 教授 田中 宏明, 准教授 平井 康宏 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The aim of this thesis is to design a desulphurization device for the fluid boiler. In the fluid boiler, fuel with extremely high sulphur content is burnt and the combustion products are not desulphurized to the required level, therefore it is necessary to build a desulphurization device. The thesis consists of two parts – theoretical and practical. In the theoretical part I stated the emission limits of sulphur dioxide, elaborated possible desulphurization methods and described the sorbets suitable for desulphurization. In the practical part I chose a dry desulphurization method with fluid reactor, to which a dry sorbent on the basis of lime hydrate is dosed. For the required parameters, I designed the whole desulphurization equipment including cloth filters, all necessary silos and major components. It is a design proposal with a layout and a spatial model.

The ozone decomposition reaction was performed in a 2.5cmx40cmx450cm two dimensional (2D) catalytic fluidized bed reactor. Commercial FCC catalyst impregnated with Fe2O3 was used at superficial gas velocities ranging between 0.006 m/s and 0.55 m/s. The onset velocity of the turbulent regime (uc) was determined as 0.4 m/s. The catalyst activity was optimized so that the effect of inter-phase mass transfer could be accentuated in the conversion reading. It was found that the general bubbling-turbulent model of Thompson et. al. (1999) combined with the mass transfer correlations of Kunii and Levenspiel (1991), Foka et. al. (1996) and Miyauchi et. al. (1980)gave reasonable predictions of the experimental data. The gradual improvement of reactor performance with an increase in superficial velocity (as predicted by the Thompson et. al. model) was not observed; instead a discontinuity of the reactor performance was noted in the vicinity of uc. More experimental work is required to substantiate this observation. Copyright / Dissertation (MEng)--University of Pretoria, 2009. / Chemical Engineering / unrestricted

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Producing gasoline-type fuels from lignocellulosic biomass has two advantages over producing alcohol-type fuels from plant sugars: gasoline has superior fuel characteristics and plant lignin/cellulose does not compete with human food supplies. A promising technology for converting lignocellulose to fuel is catalytic fast pyrolysis (CFP). The process involves injecting finely ground biomass into a fluidized bed reactor (FBR) at high temperatures, which reduce the biomass to gases that react inside the catalyst particles. This entails complex hydrodynamics to efficiently mix a stream of biomass into a catalyst bed that is fluidized by a separate stream of inert gas. Understanding the hydrodynamics is complicated by the fact that the entire process occurs inside a heavily insulated, opaque, reactor vessel. Numerical simulations offer a promising approach to understanding, predicting, and optimizing hydrodynamic mixing in a CFP biomass reactor. The purpose of this research is to understand the simulation techniques and statistical measures appropriate for quantifying mixing in a CFP biomass reactor. The methodology is validated against the canonical configuration of a non-reacting, single-inlet fluidized bed. A new finding is that the minimum bubbling velocity may be predicted by a significant increase in temporal variance of the pressure drop. The methodology is then applied to a non-canonical FBR in which biomass is injected into the catalyst bed via a vertical center tube. Since no hydrodynamic mixing data exist from laboratory experiments, mixing is inferred from the aromatics yield from the laboratory reactor. Flow configurations with which simulations demonstrate the best mixing have the highest aromatic yields in the experiments. The simulations indicate that when the bed is in the bubbling regime, the gasified biomass from the center tube is efficiently mixed radially throughout the catalyst bed. If the flow rate of inert gas is insufficient to bubble the bed, then the gasified biomass exits the center tube, reverses direction, and flows upward along the tube's outside wall. Provided the bed is bubbling due to the inert gas stream, the upper limit on the flow through the center tube, and thus the aromatic yield potential, has yet to be determined.

Groundwater (GW) accounting for most of the freshwater available around the World, finding sustainable techniques to depollute it is of crucial importance for safe drinking water supply. The extensive use of fertilizers in the agriculture, as well as other anthropogenic activities, are contributing to the excessive nitrate levels in some aquifers. These levels need to be reduced to obtain potable water. Bioelectrochemical systems (BES), using microorganisms to catalyze a desired electrochemical reaction, recently proved to be a very promising technology for water remediation. Groundwater denitrification using Microbial Electrolysis Cell (MEC) needs to be improved for further scaled-up on-site system. The advantages conferred by fluidized bed reactor (FBR), as well as the outstanding electrochemical properties of reduced graphene oxide (rGO), are two potential enhancements of such bioelectrochemical denitrification system that were investigated in this thesis. Some essential parameters could be determined during the preliminary steps' experiments. The fluidization trials gave us a clear insight that Coconut-based Activated Carbon (CAC) particles were resistant carrier particles, nicely fluidized within a 39.27cm3 circular cathodic chamber for a flow rate ranging between 450ml/min to 590ml/min. For the same flow rate of 500ml/min, we could obtain CAC particles fluidization for the upstream fluidized configuration, and still bed particles for the fixed bed downstream configuration, which would be very useful for later unbiased comparison. The denitrifying bacteria showed during their enrichment, a nitrate removal rate of up to 1.986ppm NO3-N/h in serum bottles, with an average of 0.38ppm NO2-N/h accumulation. The parallel running of fixed bed versus fluidized bed denitrifying reactor in order to compare their denitrification performances, was planned, but could not be performed due to COVID-19. The graphene oxide (GO) batch experiments showed a good biocompatibility between GO/rGO and our autotrophic denitrifying bacteria. A change of morphology within about 20 hours was observed, probably suggesting the reduction of GO to rGO by the bacteria. During a first test, the presence of GO led to a 2.7 folds less efficient denitrification performance as compared with the GO/rGO-free condition, likely due to the competition between nitrate and GO for being reduced. However, the denitrification rate in presence of GO/rGO increased up to 1.873ppm NO3-N/h after the second pulse of groundwater and flush with H2/CO2 gas, which is almost 2.3 folds higher than initially in the same condition. This suggests that GO needs some time to get fully reduced to rGO, and the denitrification rate might reach the same or higher levels as in the GO/rGO-free conditions, when GO is fully reduced. Improved denitrification would indicate that rGO facilitates the electron transfer between bacteria and nitrate, as it can be expected from its electrochemical properties previously studied. This would be worth being investigated in the scope of a longer experience. / Grundvatten (GW) som står för det mesta av det sötvatten som finns tillgängligt runt om i världen och att hitta hållbara tekniker för att förorena det är av avgörande betydelse för en trygg dricksvattenförsörjning. Den omfattande användningen av gödselmedel i jordbruket, liksom andra antropogena aktiviteter, bidrar till de överdrivna nitratnivåerna i vissa vattenfiskare. Dessa nivåer måste sänkas för att erhålla dricksvatten. Bioelektrokemiska system (BES), med användning av mikroorganismer för att katalysera en önskad elektrokemisk reaktion, visade sig nyligen vara en mycket lovande teknik för sanering av vatten. Grundvatten denitrifikation med hjälp av Microbial Electrolysis Cell (MEC) måste förbättras för att ytterligare skala upp systemet på plats. Fördelarna med fluidiserad bäddreaktor (FBR) såväl som de enastående elektrokemiska egenskaperna hos reducerad grafenoxid (rGO) är två potentiella förbättringar av ett sådant bioelektrokemiskt denitrifikationssystem som undersöktes i denna avhandling. Vissa väsentliga parametrar kan bestämmas under de preliminära stegens experiment. Fluidiseringsstudierna gav oss en klar insikt om att kokosnötbaserade aktiverade kolpartiklar (CAC) -partiklar var resistenta bärarpartiklar, trevligt fluidiserade i en cirkulär katodisk kammare på 39,27 cm3 för en flödeshastighet mellan 450ml/min till 590ml/min. För samma flödeshastighet på 500ml/min kunde vi få CAC-partikelfluidisering för uppströms fluidiserad konfiguration och stillbäddspartiklar för den fixerade bädden nedströms konfiguration, vilket skulle vara mycket användbart för senare opartisk jämförelse. De denriffriserande bakterierna visade under deras anrikning en nitratborttagningshastighet av upp till 1,986 ppm NO3-N/h i serumflaskor, med ett genomsnitt på 0,38 ppm NO2-N / h ackumulering. Den parallella körningen av denitrifierande reaktorn med fast bädd kontra fluidiserad bädd för att jämföra deras denitrifikationsprestanda planerades, men kunde inte utföras på grund av COVID-19. Diagramexperimenten av grafenoxid (GO) visade en god biokompatibilitet mellan GO/rGO och våra autotrofiska denitrifierande bakterier. En förändring av morfologin inom cirka 20 timmar observerades, vilket antagligen antydde att bakterierna minskade GO till rGO. Under ett första test ledde närvaron av GO till 2,7 gånger mindre effektiv denitrifikationsprestanda jämfört med GO/rGO-fritt tillstånd, troligtvis på grund av konkurrensen mellan nitrat och GO för att ha minskat. Denitrifikationsgraden i närvaro av GO/rGO ökade emellertid upp till 1,873 ppm NO3-N/h efter den andra grundvattenspulsen och spolades med H2/CO2-gas, vilket är nästan 2,3 gånger högre än ursprungligen i samma tillstånd. Detta antyder att GO behöver lite tid för att helt reduceras till rGO, och denitrifikationsgraden kan nå samma eller högre nivåer som i GO/rGO-fria förhållanden, när GO är helt reducerad. Förbättrad denitrifikation skulle indikera att rGO underlättar elektronöverföring mellan bakterier och nitrat, som det kan förväntas av dess elektrokemiska egenskaper som tidigare studerats. Detta skulle vara värt att undersökas inom ramen för en längre upplevelse.

Yes / Fluidized catalytic cracking (FCC) is regarded one of the most significant operations in the oil refining industries to convert feedstock (mainly vacuum gasoil) to valuable products (namely gasoline and diesel). The behavior of the fluidized catalytic cracking process is playing a main part on the overall benefits of refinery units and improving in process or control of fluidized catalytic cracking plants will result in exciting benefits economically. According to these highlights, this study is aimed to develop a new mathematical model for the FCC process taking into account the complex hydrodynamics of the reactor regenerator system with a new six lumps kinetic model for the riser. The mathematical model, simulation and optimization have done utilizing vacuum gas oil (VGO) as a feedstock and zeolite as a catalyst under the following operating conditions: temperature (733K, 783K, and 813K), weight hourly space velocity (5, 20 and 30hr−1) and catalyst to oil ratio (4, 7 and 10). The best kinetic parameters of the relevant reactions are estimated using the optimization technique based on the experimental results taken from literature. The effect of operating condition (mainly, reaction temp (T), catalyst to oil ratio (CTO) and weight hourly space velocity (WHSV) on the product composition has also been discussed. The optimal kinetic parameters obtained from the pilot plant scale have been employed to develop an industrial FCC process, where optimal operating condition based on maximum conversion of VGO with minimum cost in addition to maximizing the octane number of gasoline (GLN), have been studied. Minimum coke content deposition the catalyst within the regenerator is also investigated here. New results (the highest conversion and octane number, and the lowest coke content) have obtained in comparison with those reported in the literature.