Effect of cycle time and airflow in biological nitrogen removal from poultry slaughterhouse wastewater using sequencing batch reactor

This study aimed to evaluate the influence of airflow (0.25, 0.50 and 0.75 L.L-1.min-1) and cycle time (10.45 h, 14.25 h and 17.35 h) on a sequencing batch reactor (SBR) performance in promoting nitrification and denitrification of poultry slaughterhouse wastewater. The operational stages included feeding, aerobic and anoxic reactions, sedimentation and discharge. SBR was operated in a laboratory scale with a working volume of 4 L, keeping 25% of biomass retained inside the reactor as inoculum for the next batch. In the anoxic stage, C: N ratio was maintained between 5 and 6 by adding cassava starch wastewater. A factorial design (22) with five repetitions was designed at the central point to evaluate the influence of cycle time and airflow on total inorganic nitrogen removal (N-NH4++N-NO2-+N-NO3-) and in the whole process (nitrification and denitrification). The highest total inorganic nitrogen removal (93.3%) was observed for airflow of 0.25 L.L-1.min‑1 and a cycle time of 14.25 h. At the end of the experiment, the sludge inside the reactor was characterized by fluorescent in situ hybridization (FISH), indicating the presence of ammonia and nitrite oxidizing bacteria.

Modelling of calciner in post-combustion carbon capture process

Climate change has given an impetus to research and developed new technologies to reduce significantly carbon dioxide emissions in energy production in the developed countries. The major pollution source, fossil fuels, will be used as an energy source for many decades, which provides the demand for carbon capture and storage technologies. Over recent years many new technologies has been developed and one of the most promising is calcium-looping in post-combustion carbon capture process, which use carbonation-calcination cycle to capture carbon dioxide from the flue gas of a combustion process. First pilot plant for calcium-looping process has been built in Oviedo, Spain. In this study, a three-dimensional model has been created for the calciner, which is one of the two fluidized bed reactors needed for the process. The calciner is a regenerator where the captured carbon dioxide is removed from the calcium material and then collected after the reactor. Thesis concentrates in creating the calciner 3D-model frame with CFB3D-program and testing the model with two different example cases. Used input parameters and calciner geometry are Oviedo pilot plant design parameters. The calculation results give information about the process and show that pilot plant calciner should perform as planned. This Master’s Thesis is done in participation to EU FP7 project CaOling.

Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

Validation of a 3D model for oxygen combustion in a circulating fluidized bed

In this thesis, a model called CFB3D is validated for oxygen combustion in circulating fluidized bed boiler. The first part of the work consists of literature review in which circulating fluidized bed and oxygen combustion technologies are studied. In addition, the modeling of circulating fluidized bed furnaces is discussed and currently available industrial scale three-dimensional furnace models are presented. The main features of CFB3D model are presented along with the theories and equations related to the model parameters used in this work. The second part of this work consists of the actual research and modeling work including measurements, model setup, and modeling results. The objectives of this thesis is to study how well CFB3D model works with oxygen combustion compared to air combustion in circulating fluidized bed boiler and what model parameters need to be adjusted when changing from air to oxygen combustion. The study is performed by modeling two air combustion cases and two oxygen combustion cases with comparable boiler loads. The cases are measured at Ciuden 30 MWth Flexi-Burn demonstration plant in April 2012. The modeled furnace temperatures match with the measurements as well in oxygen combustion cases as in air combustion cases but the modeled gas concentrations differ from the measurements clearly more in oxygen combustion cases. However, the same model parameters are optimal for both air and oxygen combustion cases. When the boiler load is changed, some combustion and heat transfer related model parameters need to be adjusted. To improve the accuracy of modeling results, better flow dynamics model should be developed in the CFB3D model. Additionally, more measurements are needed from the lower furnace to find the best model parameters for each case. The validation work needs to be continued in order to improve the modeling results and model predictability.

Limestone Reactions in a Fluidized Bed Heat Exchanger of an Oxy-fuel Circulating Fluidized Bed Boiler

Oxy-fuel combustion in a circulating fluidized bed (CFB) boiler appears to be a promising option for capturing CO2 in power plants. Oxy-fuel combustion is based on burning of fuel in the mixture of oxygen and re-circulated flue gas instead of air. Limestone (CaCO3) is typically used for capturing of SO2 in CFB boilers where limestone calcines to calcium oxide (CaO). Because of high CO2 concentration in oxy-fuel combustion, calcination reaction may be hindered or carbonation, the reverse reaction of calcination, may occur. Carbonation of CaO particles can cause problems especially in the circulation loop of a CFB boiler where temperature level is lower than in the furnace. The aim of the thesis was to examine carbonation of CaO in a fluidized bed heat exchanger of a CFB boiler featuring oxy-fuel combustion. The calculations and analyzing were based on measurement data from an oxy-fuel pilot plant and on 0-dimensional (0D) gas balance of a fluidized bed heat exchanger. Additionally, the objective was to develop a 1-dimensional (1D) model of a fluidized bed heat exchanger by searching a suitable pre-exponential factor for a carbonation rate constant. On the basis of gas measurement data and the 0D gas balance, it was found that the amount of fluidization gas decreased as it flew through the fluidized bed heat exchanger. Most likely the reason for this was carbonation of CaO. It was discovered that temperature has a promoting effect on the reaction rate of carbonation. With the 1D model, a suitable pre-exponential factor for the equation of carbonation rate constant was found. However, during measurements there were several uncertainties, and in the calculations plenty of assumptions were made. Besides, the temperature level in the fluidized bed heat exchanger was relatively low during the measurements. Carbonation should be considered when fluidized bed heat exchangers and the capacity of related fans are designed for a CFB boiler with oxy-fuel combustion.

Mathematical modeling of laboratory scale three-phase fixed bed reactors

Detta arbete fokuserar på modellering av katalytiska gas-vätskereaktioner som genomförs i kontinuerliga packade bäddar. Katalyserade gas-vätskereaktioner hör till de mest typiska reaktionerna i kemisk industri; därför behandlas här packade bäddreaktorer som ett av de populäraste alternativen, då kontinuerlig drift eftersträvas. Tack vare en stor katalysatormängd per volym har de en kompakt struktur, separering av katalysatorn behövs inte och genom en professionell design kan den mest fördelaktiga strömningsbilden upprätthållas i reaktorn. Packade bäddreaktorer är attraktiva p.g.a. lägre investerings- och driftskostnader. Även om packade bäddar används intensivt i industri, är det mycket utmanande att modellera. Detta beror på att tre faser samexisterar och systemets geometri är komplicerad. Existensen av flera reaktioner gör den matematiska modelleringen även mera krävande. Många förenklingar blir därmed nödvändiga. Modellerna involverar typiskt flera parametrar som skall justeras på basis av experimentella data. I detta arbete studerades fem olika reaktionssystem. Systemen hade studerats experimentellt i vårt laboratorium med målet att nå en hög produktivitet och selektivitet genom ett optimalt val av katalysatorer och driftsbetingelser. Hydrering av citral, dekarboxylering av fettsyror, direkt syntes av väteperoxid samt hydrering av sockermonomererna glukos och arabinos användes som exempelsystem. Även om dessa system hade mycket gemensamt, hade de också unika egenskaper och krävde därför en skräddarsydd matematisk behandling. Citralhydrering var ett system med en dominerande huvudreaktion som producerar citronellal och citronellol som huvudprodukter. Produkterna används som en citrondoftande komponent i parfymer, tvålar och tvättmedel samt som plattform-kemikalier. Dekarboxylering av stearinsyra var ett specialfall, för vilket en reaktionsväg för produktion av långkedjade kolväten utgående från fettsyror söktes. En synnerligen hög produktselektivitet var karakteristisk för detta system. Även processuppskalning modellerades för dekarboxylerings-reaktionen. Direkt syntes av väteperoxid hade som målsättning att framta en förenklad process att producera väteperoxid genom att låta upplöst väte och syre reagera direkt i ett lämpligt lösningsmedel på en aktiv fast katalysator. I detta system förekommer tre bireaktioner, vilka ger vatten som oönskad produkt. Alla dessa tre reaktioner modellerades matematiskt med hjälp av dynamiska massbalanser. Målet med hydrering av glukos och arabinos är att framställa produkter med en hög förädlingsgrad, nämligen sockeralkoholer, genom katalytisk hydrering. För dessa två system löstes ämnesmängd- och energibalanserna simultant för att evaluera effekter inne i porösa katalysatorpartiklar. Impulsbalanser som bestämmer strömningsbetingelser inne i en kemisk reaktor, ersattes i alla modelleringsstudier med semi-empiriska korrelationsuttryck för vätskans volymandel och tryckförlust och med axiell dispersionsmodell för beskrivning av omblandningseffekter. Genom att justera modellens parametrar kunde reaktorns beteende beskrivas väl. Alla experiment var genomförda i laboratorieskala. En stor mängd av kopplade effekter samexisterade: reaktionskinetik inklusive adsorption, katalysatordeaktivering, mass- och värmeöverföring samt strömningsrelaterade effekter. En del av dessa effekter kunde studeras separat (t.ex. dispersionseffekter och bireaktioner). Inverkan av vissa fenomen kunde ibland minimeras genom en noggrann planering av experimenten. På detta sätt kunde förenklingar i modellerna bättre motiveras. Alla system som studerades var industriellt relevanta. Utveckling av nya, förenklade produktionsteknologier för existerande kemiska komponenter eller nya komponenter är ett gigantiskt uppdrag. Studierna som presenterades här fokuserade på en av den teknisk-vetenskapliga utfärdens första etapper.

Fast pyrolysis in circulating fluidized bed: feasibility study

Today the limitedness of fossil fuel resources is clearly realized. For this reason there is a strong focus throughout the world on shifting from fossil fuel based energy system to biofuel based energy system. In this respect Finland with its proven excellent forestry capabilities has a great potential to accomplish this goal. It is regarded that one of the most efficient ways of wood biomass utilization is to use it as a feedstock for fast pyrolysis process. By means of this process solid biomass is converted into liquid fuel called bio-oil which can be burnt at power plants, used for hydrogen generation through a catalytic steam reforming process and as a source of valuable chemical compounds. Nowadays different configurations of this process have found their applications in several pilot plants worldwide. However the circulating fluidized bed configuration is regarded as the one with the highest potential to be commercialized. In the current Master’s Thesis a feasibility study of circulating fluidized bed fast pyrolysis process utilizing Scots pine logs as a raw material was conducted. The production capacity of the process is 100 000 tonne/year of bio-oil. The feasibility study is divided into two phases: a process design phase and economic feasibility analysis phase. The process design phase consists of mass and heat balance calculations, equipment sizing, estimation of pressure drops in the pipelines and development of plant layout. This phase resulted in creation of process flow diagrams, equipment list and Microsoft Excel spreadsheet that calculates the process mass and heat balances depending on the bio-oil production capacity which can be set by a user. These documents are presented in the current report as appendices. In the economic feasibility analysis phase there were at first calculated investment and operating costs of the process. Then using these costs there was calculated the price of bio-oil which is required to reach the values of internal rate of return of 5%, 10%, 20%, 30%, 40%, and 50%.

Fluid dynamic modelling and simulation of circulating fluidized bed reactors: importance of the interface turbulence transfer

The main objective of this work is to analyze the importance of the gas-solid interface transfer of the kinetic energy of the turbulent motion on the accuracy of prediction of the fluid dynamic of Circulating Fluidized Bed (CFB) reactors. CFB reactors are used in a variety of industrial applications related to combustion, incineration and catalytic cracking. In this work a two-dimensional fluid dynamic model for gas-particle flow has been used to compute the porosity, the pressure, and the velocity fields of both phases in 2-D axisymmetrical cylindrical co-ordinates. The fluid dynamic model is based on the two fluid model approach in which both phases are considered to be continuous and fully interpenetrating. CFB processes are essentially turbulent. The model of effective stress on each phase is that of a Newtonian fluid, where the effective gas viscosity was calculated from the standard k-epsilon turbulence model and the transport coefficients of the particulate phase were calculated from the kinetic theory of granular flow (KTGF). This work shows that the turbulence transfer between the phases is very important for a better representation of the fluid dynamics of CFB reactors, especially for systems with internal recirculation and high gradients of particle concentration. Two systems with different characteristics were analyzed. The results were compared with experimental data available in the literature. The results were obtained by using a computer code developed by the authors. The finite volume method with collocated grid, the hybrid interpolation scheme, the false time step strategy and SIMPLEC (Semi-Implicit Method for Pressure Linked Equations - Consistent) algorithm were used to obtain the numerical solution.

A Test Bed Applied Mobile Robot Navigation

It is presented a test bed applied to studies on dynamics, control, and navigation of mobile robots. A cargo ship scale model was chosen, which can be radio-controlled or operated autonomously through an embedded control system. A control program, which manages on board mission execution, is implemented on a microcontroller. Navigation is based on an electronic compass, which includes automatic compensation for pitch and roll motions. Heading control loop is based on this sensor, and on a rudder positioning system. A propulsion control system is also implemented. Typical manoeuvres as the turning test and "zig-zag", were implemented and tested. They are included on a manoeuvre library, and can be accessed independently or in combined modes. The embedded system is also in charge of signal acquisition and storing during the missions. It is possible to analyse experiments on identification of ship dynamics, control, and navigation, through the data transferred to a PC by serial communication. Navigation is going to be improved by including inertial sensors on board, and a DGPS. Preliminary tests are aimed to ship identification, and manoeuvrability, using free model tests. Future steps include extending this system for developing other mobile robots as, ROVs, AUVs, and aerial vehicles.

Sorbent characterization for circulating fluidized bed scrubbers

Harmful sulfur dioxide (SO2) emissions from power plants have increasingly been restricted since the 1970’s. Circulating fluidized bed (CFB) scrubber is a dry flue gas desulfurization method of absorbing SO2 out of the flue gas with sorbent. In current commercial plants, the used sorbent is commercial or on-site hydrated calcium hydroxide. The CFB scrubber process is characterized by a close but adequate approach to the flue gas saturation temperature that is achieved by spraying water to the absorber followed by a particulate control device. Very high SO2 removal is achieved along with a dry byproduct that is continuously recirculated back to the absorber for enhanced sorbent utilization. The aim of this work is to develop a method that would characterize the reactivity of sorbents used in CFB scrubbers and to conclude how different process parameters and sorbent properties affect the sulfur absorption. The developed characterization method is based on a fixed bed of sorbent and inert silica sand, through which an SO2 containing gas mixture is led. The reaction occurs in the bed and the SO2 concentration in the outlet as a function of time, a breakthrough curve, is obtained from the analyzer. Reactivity of the sorbents are evaluated by the absorbed sulfur amount. Results suggest that out of process parameters, lower SO2 concentration, lower temperature and higher moisture content enhance the desulfurization. Between different sorbents, specific surface area seems to be the most significant parameter. Large surface area linearly leads to more efficient desulfurization. Overall, the solid conversion levels in the tests were very low creating uncertainty to the validity of the results. New desing is being planned to overcome the problems of the device.

Characterisation of waste for combustion : with special reference to the role of zinc

Waste combustion has gone from being a volume reducing discarding-method to an energy recovery process for unwanted material that cannot be reused or recycled. Different fractions of waste are used as fuel today, such as; municipal solid waste, refuse derived fuel, and solid recovered fuel. Furthermore, industrial waste, normally a mixture between commercial waste and building and demolition waste, is common, either as separate fuels or mixed with, for example, municipal solid waste. Compared to fossil or biomass fuels, waste mixtures are extremely heterogeneous, making it a complicated fuel. Differences in calorific values, ash content, moisture content, and changing levels of elements, such as Cl and alkali metals, are common in waste fuel. Moreover, waste contains much higher levels of troublesome trace elements, such as Zn, which is thought to accelerate a corrosion process. Varying fuel quality can be strenuous on the boiler system and may cause fouling and corrosion of heat exchanger surfaces. This thesis examines waste fuels and waste combustion from different angles, with the objective of giving a better understanding of waste as an important fuel in today’s fuel economy. Several chemical characterisation campaigns of waste fuels over longer time periods (10-12 months) was used to determine the fossil content of Swedish waste fuels, to investigate possible seasonal variations, and to study the presence of Zn in waste. Data from the characterisation campaigns were used for thermodynamic equilibrium calculations to follow trends and determine the effect of changing concentrations of various elements. The thesis also includes a study of the thermal behaviour of Zn and a full—scale study of how the bed temperature affects the volatilisation of alkali metals and Zn from the fuel. As mixed waste fuel contains considerable amounts of fresh biomass, such as wood, food waste, paper etc. it would be wrong to classify it as a fossil fuel. When Sweden introduced waste combustion as a part of the European Union emission trading system in the beginning of 2013 there was a need for combustion plants to find a usable and reliable method to determine the fossil content. Four different methods were studied in full-scale of seven combustion plants; 14Canalysis of solid waste, 14C-analysis of flue gas, sorting analysis followed by calculations, and a patented balance method that is using a software program to calculate the fossil content based on parameters from the plant. The study showed that approximately one third of the coal in Swedish waste mixtures has fossil origins and presented the plants with information about the four different methods and their advantages and disadvantages. Characterisation campaigns also showed that industrial waste contain higher levels of trace elements, such as Zn. The content of Zn in Swedish waste fuels was determined to be approximately 800 mg kg-1 on average, based on 42 samples of solid waste from seven different plants with varying mixtures between municipal solid waste and industrial waste. A review study of the occurrence of Zn in fuels confirmed that the highest amounts of Zn are present in waste fuels rather than in fossil or biomass fuels. In tires, Zn is used as a vulcanizing agent and can reach concentration values of 9600-16800 mg kg-1. Waste Electrical and Electronic Equipment is the second Zn-richest fuel and even though on average Zn content is around 4000 mg kg-1, the values of over 19000 mg kg-1 were also reported. The increased amounts of Zn, 3000-4000 mg kg-1, are also found in municipal solid waste, sludge with over 2000 mg kg-1 on average (some exceptions up to 49000 mg kg-1), and other waste derived fuels (over 1000 mg kg-1). Zn is also found in fossil fuels. In coal, the average level of Zn is 100 mg kg-1, the higher amount of Zn was only reported for oil shale with values between 20-2680 mg kg-1. The content of Zn in biomass is basically determined by its natural occurrence and it is typically 10-100 mg kg-1. The thermal behaviour of Zn is of importance to understand the possible reactions taking place in the boiler. By using thermal analysis three common Zn-compounds were studied (ZnCl2, ZnSO4, and ZnO) and compared to phase diagrams produced with thermodynamic equilibrium calculations. The results of the study suggest that ZnCl2(s/l) cannot exist readily in the boiler due to its volatility at high temperatures and its conversion to ZnO in oxidising conditions. Also, ZnSO4 decomposes around 680°C, while ZnO is relatively stable in the temperature range prevailing in the boiler. Furthermore, by exposing ZnO to HCl in a hot environment (240-330°C) it was shown that chlorination of ZnO with HCl gas is possible. Waste fuel containing high levels of elements known to be corrosive, for example, Na and K in combination with Cl, and also significant amounts of trace elements, such as Zn, are demanding on the whole boiler system. A full-scale study of how the volatilisation of Na, K, and Zn is affected by the bed temperature in a fluidised bed boiler was performed parallel with a lab-scale study with the same conditions. The study showed that the fouling rate on deposit probes were decreased by 20 % when the bed temperature was decreased from 870°C to below 720°C. In addition, the lab-scale experiments clearly indicated that the amount of alkali metals and Zn volatilised depends on the reactor temperature.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Computational studies for the design of process equipment with complex geometries

This study combines several projects related to the flows in vessels with complex shapes representing different chemical apparata. Three major cases were studied. The first one is a two-phase plate reactor with a complex structure of intersecting micro channels engraved on one plate which is covered by another plain plate. The second case is a tubular microreactor, consisting of two subcases. The first subcase is a multi-channel two-component commercial micromixer (slit interdigital) used to mix two liquid reagents before they enter the reactor. The second subcase is a micro-tube, where the distribution of the heat generated by the reaction was studied. The third case is a conventionally packed column. However, flow, reactions or mass transfer were not modeled. Instead, the research focused on how to describe mathematically the realistic geometry of the column packing, which is rather random and can not be created using conventional computeraided design or engineering (CAD/CAE) methods. Several modeling approaches were used to describe the performance of the processes in the considered vessels. Computational fluid dynamics (CFD) was used to describe the details of the flow in the plate microreactor and micromixer. A space-averaged mass transfer model based on Fick’s law was used to describe the exchange of the species through the gas-liquid interface in the microreactor. This model utilized data, namely the values of the interfacial area, obtained by the corresponding CFD model. A common heat transfer model was used to find the heat distribution in the micro-tube. To generate the column packing, an additional multibody dynamic model was implemented. Auxiliary simulation was carried out to determine the position and orientation of every packing element in the column. This data was then exported into a CAD system to generate desirable geometry, which could further be used for CFD simulations. The results demonstrated that the CFD model of the microreactor could predict the flow pattern well enough and agreed with experiments. The mass transfer model allowed to estimate the mass transfer coefficient. Modeling for the second case showed that the flow in the micromixer and the heat transfer in the tube could be excluded from the larger model which describes the chemical kinetics in the reactor. Results of the third case demonstrated that the auxiliary simulation could successfully generate complex random packing not only for the column but also for other similar cases.

Modeling of temperature regimes in a furnace of bubbling fluidized bed boiler

The work is mainly focused on the technology of bubbling fluidized bed combustion. Heat transfer and hydrodynamics of the process were examined in the work in detail. Special emphasis was placed on the process of heat exchange in a freeboard zone of bubbling fluidized bed boiler. Operating mode of bubbling fluidized bed boiler depends on many parameters. To assess the influence of some parameters on a temperature regime inside the furnace a simplified method of zonal modeling was used in the work. Thus, effects of bed material fineness, excess air ratio and changes in boiler load were studied. Besides the technology of combustion in bubbling fluidized bed, other common technologies of solid fuels combustion were reviewed. In addition, brief survey of most widely used types of solid fuel was performed in the work.