Simulation of hydrogen peroxide direct synthesis in a microreactor

A set of models in Aspen plus was built to simulate the direct synthesis process of hydrogen peroxide in a micro-reactor system. This process model can be used to carry out material balance calculation under various experimental conditions. Three thermodynamic property methods were compared by calculating gas solubility and Uniquac-RK method was finally selected for process model. Two different operation modes with corresponding operation conditions were proposed as the starting point of future experiments. Simulations for these two modes were carried out to get the information of material streams. Moreover, some hydrodynamic parameters such as gas/liquid superficial velocity, gas holdup were also calculated with improved process model. These parameters proved the proposed experimental conditions reasonable to some extent. The influence of operation conditions including temperature, pressure and circulation ratio was analyzed for the first operation mode, where pure oxygen was fed into dissolving tank and hydrogen-carbon dioxide mixture was fed into microreactor directly. The preferred operation conditions for the system are low temperature (2°C) and high pressure (30 bar) in dissolving tank. High circulation ratio might be good in the sense that more oxygen could be dissolved and fed into reactor for reactions, but meanwhile hydrodynamics of microreactor should be considered. Furthermore, more operation conditions of reactor gas/liquid feeds in both of two operation modes were proposed to provide guidance for future experiment design and corresponding hydrodynamic parameters were also calculated. Finally, safety issue was considered from thermodynamic point of view and there is no explosion danger at given experimental plan since the released reaction heat will not cause solvent vaporization inside the microchannels. The improvement of process model still needs further study based on the future experimental results.

Design Aspects of Megawatt-Range Direct-Driven Permanent MagnetWind Generators

Direct-driven permanent magnet synchronous generator is one of the most promising topologies for megawatt-range wind power applications. The rotational speed of the direct-driven generator is very low compared with the traditional electrical machines. The low rotational speed requires high torque to produce megawatt-range power. The special features of the direct-driven generators caused by the low speed and high torque are discussed in this doctoral thesis. Low speed and high torque set high demands on the torque quality. The cogging torque and the load torque ripple must be as low as possible to prevent mechanical failures. In this doctoral thesis, various methods to improve the torque quality are compared with each other. The rotor surface shaping, magnet skew, magnet shaping, and the asymmetrical placement of magnets and stator slots are studied not only by means of torque quality, but also the effects on the electromagnetic performance and manufacturability of the machine are discussed. The heat transfer of the direct-driven generator must be designed to handle the copper losses of the stator winding carrying high current density and to keep the temperature of the magnets low enough. The cooling system of the direct-driven generator applying the doubly radial air cooling with numerous radial cooling ducts was modeled with a lumped-parameter-based thermal network. The performance of the cooling system was discussed during the steady and transient states. The effect of the number and width of radial cooling ducts was explored. The large number of radial cooling ducts drastically increases the impact of the stack end area effects, because the stator stack consists of numerous substacks. The effects of the radial cooling ducts on the effective axial length of the machine were studied by analyzing the crosssection of the machine in the axial direction. The method to compensate the magnet end area leakage was considered. The effect of the cooling ducts and the stack end area effects on the no-load voltages and inductances of the machine were explored by using numerical analysis tools based on the three-dimensional finite element method. The electrical efficiency of the permanent magnet machine with different control methods was estimated analytically over the whole speed and torque range. The electrical efficiencies achieved with the most common control methods were compared with each other. The stator voltage increase caused by the armature reaction was analyzed. The effect of inductance saturation as a function of load current was implemented to the analytical efficiency calculation.

CFD Modelling of Direct Contact Condensation in Suppression Pools by Applying Condensation Models of Separated Flow

The condensation rate has to be high in the safety pressure suppression pool systems of Boiling Water Reactors (BWR) in order to fulfill their safety function. The phenomena due to such a high direct contact condensation (DCC) rate turn out to be very challenging to be analysed either with experiments or numerical simulations. In this thesis, the suppression pool experiments carried out in the POOLEX facility of Lappeenranta University of Technology were simulated. Two different condensation modes were modelled by using the 2-phase CFD codes NEPTUNE CFD and TransAT. The DCC models applied were the typical ones to be used for separated flows in channels, and their applicability to the rapidly condensing flow in the condensation pool context had not been tested earlier. A low Reynolds number case was the first to be simulated. The POOLEX experiment STB-31 was operated near the conditions between the ’quasi-steady oscillatory interface condensation’ mode and the ’condensation within the blowdown pipe’ mode. The condensation models of Lakehal et al. and Coste & Lavi´eville predicted the condensation rate quite accurately, while the other tested ones overestimated it. It was possible to get the direct phase change solution to settle near to the measured values, but a very high resolution of calculation grid was needed. Secondly, a high Reynolds number case corresponding to the ’chugging’ mode was simulated. The POOLEX experiment STB-28 was chosen, because various standard and highspeed video samples of bubbles were recorded during it. In order to extract numerical information from the video material, a pattern recognition procedure was programmed. The bubble size distributions and the frequencies of chugging were calculated with this procedure. With the statistical data of the bubble sizes and temporal data of the bubble/jet appearance, it was possible to compare the condensation rates between the experiment and the CFD simulations. In the chugging simulations, a spherically curvilinear calculation grid at the blowdown pipe exit improved the convergence and decreased the required cell count. The compressible flow solver with complete steam-tables was beneficial for the numerical success of the simulations. The Hughes-Duffey model and, to some extent, the Coste & Lavi´eville model produced realistic chugging behavior. The initial level of the steam/water interface was an important factor to determine the initiation of the chugging. If the interface was initialized with a water level high enough inside the blowdown pipe, the vigorous penetration of a water plug into the pool created a turbulent wake which invoked the chugging that was self-sustaining. A 3D simulation with a suitable DCC model produced qualitatively very realistic shapes of the chugging bubbles and jets. The comparative FFT analysis of the bubble size data and the pool bottom pressure data gave useful information to distinguish the eigenmodes of chugging, bubbling, and pool structure oscillations.

Marketing-Sales Cooperation and its Relation on Direct Sales Performance: an Example of a Medium-sized Oil Company

The study touches upon marketing-sales departments’ cooperation and investigates marketing-sales cooperative model within the case company. So that research increases understanding of linkages between Marketing and Sales departments with an illustrative example of Russian medium-sized oil company (LLC Neste St. Petersburg), the subsidiary of Finnish-based Neste Oil. The empirical study is done from marketing and sales perspectives. And for sales main attention was brought to direct sales, both B2B and B2C. Research considers all five domains of cooperation, and among others, study reveals the attitude towards external (market) and internal (product) knowledge, and its mutual use by marketing and sales managers. A qualitative research method, participant observations, and in-depth interviews with upper-management made it possible to explore all facets of joint work. Moreover, research responses the changes in a model of cooperation between marketing and sales when moving from medium size to large company.

The Possibilities and Dosimetric Limitations of MLC-Based Intensity-Modulated Radiotherapy Delivery and Optimization Techniques

The use of intensity-modulated radiotherapy (IMRT) has increased extensively in the modern radiotherapy (RT) treatments over the past two decades. Radiation dose distributions can be delivered with higher conformality with IMRT when compared to the conventional 3D-conformal radiotherapy (3D-CRT). Higher conformality and target coverage increases the probability of tumour control and decreases the normal tissue complications. The primary goal of this work is to improve and evaluate the accuracy, efficiency and delivery techniques of RT treatments by using IMRT. This study evaluated the dosimetric limitations and possibilities of IMRT in small (treatments of head-and-neck, prostate and lung cancer) and large volumes (primitive neuroectodermal tumours). The dose coverage of target volumes and the sparing of critical organs were increased with IMRT when compared to 3D-CRT. The developed split field IMRT technique was found to be safe and accurate method in craniospinal irradiations. By using IMRT in simultaneous integrated boosting of biologically defined target volumes of localized prostate cancer high doses were achievable with only small increase in the treatment complexity. Biological plan optimization increased the probability of uncomplicated control on average by 28% when compared to standard IMRT delivery. Unfortunately IMRT carries also some drawbacks. In IMRT the beam modulation is realized by splitting a large radiation field to small apertures. The smaller the beam apertures are the larger the rebuild-up and rebuild-down effects are at the tissue interfaces. The limitations to use IMRT with small apertures in the treatments of small lung tumours were investigated with dosimetric film measurements. The results confirmed that the peripheral doses of the small lung tumours were decreased as the effective field size was decreased. The studied calculation algorithms were not able to model the dose deficiency of the tumours accurately. The use of small sliding window apertures of 2 mm and 4 mm decreased the tumour peripheral dose by 6% when compared to 3D-CRT treatment plan. A direct aperture based optimization (DABO) technique was examined as a solution to decrease the treatment complexity. The DABO IMRT technique was able to achieve treatment plans equivalent with the conventional IMRT fluence based optimization techniques in the concave head-and-neck target volumes. With DABO the effective field sizes were increased and the number of MUs was reduced with a factor of two. The optimality of a treatment plan and the therapeutic ratio can be further enhanced by using dose painting based on regional radiosensitivities imaged with functional imaging methods.

Loss Modelling of Three-Level Inverters controlled with Space Vector Modulation Technique

The objective of this master’s thesis is to investigate the loss behavior of three-level ANPC inverter and compare it with conventional NPC inverter. The both inverters are controlled with mature space vector modulation strategy. In order to provide the comparison both accurate and detailed enough NPC and ANPC simulation models should be obtained. The similar control model of SVM is utilized for both NPC and ANPC inverter models. The principles of control algorithms, the structure and description of models are clarified. The power loss calculation model is based on practical calculation approaches with certain assumptions. The comparison between NPC and ANPC topologies is presented based on results obtained for each semiconductor device, their switching and conduction losses and efficiency of the inverters. Alternative switching states of ANPC topology allow distributing losses among the switches more evenly, than in NPC inverter. Obviously, the losses of a switching device depend on its position in the topology. Losses distribution among the components in ANPC topology allows reducing the stress on certain switches, thus losses are equally distributed among the semiconductors, however the efficiency of the inverters is the same. As a new contribution to earlier studies, the obtained models of SVM control, NPC and ANPC inverters have been built. Thus, this thesis can be used in further more complicated modelling of full-power converters for modern multi-megawatt wind energy conversion systems.

Combination of catalyst development and chemical reaction engineering : a key aspect to improve the hydrogen peroxide direct synthesis

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Safety study of hydrogen peroxide direct synthesis

Kandidaatintyön johdantokappaleessa esitellään vetyperoksidi ja mihin sitä käytetään teollisuudessa. Työssä vertaillaan antrakinoniprosessia ja suoraa prosessia sekä selvitetään nykyisin enemmän vetyperoksidituotantoon käytetyn antrakinoniprosessin ongelmakohdat ja osoitetaan, miksi suora synteesi vetyperoksidin tuotannossa olisi parempi vaihtoehto. Kandidaatintyön käsittelee suurilta osin turvallisuusongelmia, joita esiintyy suoran synteesin yhteydessä. Kirjallisuudesta on etsitty ratkaisuja näihin ongelmiin, kuten membraaniprosessin käyttöä räjähdysvaaran välttämiseksi. Pienemmän reaktorin eli ns. mikroreaktorin käyttö tuo mukanaan monia etuja vetyperoksidin tuotantoon. Tällöin prosessi on turvallisempi ja sitä on helpompi hallita. Mikroreaktorissa voidaan käyttää korkeampia lämpötiloja ja paineita kuin makroreaktorilla ilman, että räjähdysvaara prosessissa kasvaisi. Mikroreaktorin sisällä olevat mikrokanavat luovat turvallisen ympäristön synteesille. Aspen plus – simulointiohjelmalla mallinnettiin ja simulointiin suoran prosessin kriittisiä virtoja mikroreaktorissa. Tarkoituksena oli löytää virrat, joissa kulkee mahdollisesti räjähtävä kaasuseos. Kaasumaiset prosessivirrat ovat kriittisimmät vetyperoksidin suorassa synteesissä, koska ne aiheuttavat todennäköisemmin räjähdyksen kuin nestemäiset prosessivirrat. Kaikkein eniten prosessiturvallisuutta uhkaavat ainevirrat ennen ja jälkeen mikroreaktoria.

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.

Switchable lanthanide fluorescence probes in homogenous molecular diagnostics

The number of molecular diagnostic assays has increased tremendously in recent years.Nucleic acid diagnostic assays have been developed, especially for the detection of human pathogenic microbes and genetic markers predisposing to certain diseases. Closed-tube methods are preferred because they are usually faster and easier to perform than heterogenous methods and in addition, target nucleic acids are commonly amplified leading to risk of contamination of the following reactions by the amplification product if the reactions are opened. The present study introduces a new closed-tube switchable complementation probes based PCR assay concept where two non-fluorescent probes form a fluorescent lanthanide chelate complex in the presence of the target DNA. In this dual-probe PCR assay method one oligonucleotide probe carries a non-fluorescent lanthanide chelate and another probe a light absorbing antenna ligand. The fluorescent lanthanide chelate complex is formed only when the non-fluorescent probes are hybridized to adjacent positions into the target DNA bringing the reporter moieties in close proximity. The complex is formed by self-assembled lanthanide chelate complementation where the antenna ligand is coordinated to the lanthanide ion captured in the chelate. The complementation probes based assays with time-resolved fluorescence measurement showed low background signal level and hence, relatively high nucleic acid detection sensitivity (low picomolar target concentration). Different lanthanide chelate structures were explored and a new cyclic seven dentate lanthanide chelate was found suitable for complementation probe method. It was also found to resist relatively high PCR reaction temperatures, which was essential for the PCR assay applications. A seven-dentate chelate with two unoccupied coordination sites must be used instead of a more stable eight- or nine-dentate chelate because the antenna ligand needs to be coordinated to the free coordination sites of the lanthanide ion. The previously used linear seven-dentate lanthanide chelate was found to be unstable in PCR conditions and hence, the new cyclic chelate was needed. The complementation probe PCR assay method showed high signal-to-background ratio up to 300 due to a low background fluorescence level and the results (threshold cycles) in real-time PCR were reached approximately 6 amplification cycles earlier compared to the commonly used FRET-based closed-tube PCR method. The suitability of the complementation probe method for different nucleic acid assay applications was studied. 1) A duplex complementation probe C. trachomatis PCR assay with a simple 10-minute urine sample preparation was developed to study suitability of the method for clinical diagnostics. The performance of the C. trachomatis assay was equal to the commercial C. trachomatis nucleic acid amplification assay containing more complex sample preparation based on DNA extraction. 2) A PCR assay for the detection of HLA-DQA1*05 allele, that is used to predict the risk of type 1 diabetes, was developed to study the performance of the method in genotyping. A simple blood sample preparation was used where the nucleic acids were released from dried blood sample punches using high temperature and alkaline reaction conditions. The complementation probe HLA-DQA1*05 PCR assay showed good genotyping performance correlating 100% with the routinely used heterogenous reference assay. 3) To study the suitability of the complementation probe method for direct measurement of the target organism, e.g., in the culture media, the complementation probes were applied to amplificationfree closed-tube bacteriophage quantification by measuring M13 bacteriophage ssDNA. A low picomolar bacteriophage concentration was detected in a rapid 20- minute assay. The assay provides a quick and reliable alternative to the commonly used and relatively unreliable UV-photometry and time-consuming culture based bacteriophage detection methods and indicates that the method could also be used for direct measurement of other micro-organisms. The complementation probe PCR method has a low background signal level leading to a high signal-to-background ratio and relatively sensitive nucleic acid detection. The method is compatible with simple sample preparation and it was shown to tolerate residues of urine, blood, bacteria and bacterial culture media. The common trend in nucleic acid diagnostics is to create easy-to-use assays suitable for rapid near patient analysis. The complementation probe PCR assays with a brief sample preparation should be relatively easy to automate and hence, would allow the development of highperformance nucleic acid amplification assays with a short overall assay time.

Search advertising for small Finnish tourism company in Russian Internet – Experimental study: Google AdWords versus Yandex.Direct

Yandex is the dominant search engine in Russia, followed by the world leader Google. This study focuses on the performance differences between the two in search advertising in the context of tourism, by running two identical campaigns and measuring the KPI’s, such as CPA (cost-per-action), on both campaigns. Search engine advertising is a new and fast changing form of advertising, which should be studied frequently in order to keep up with the changes. Research was done as an experimental study in cooperation with a Finnish tourism company and the data is gathered from the clickstream and not from questionnaires, which is recommended method by the literature. The results of the study suggests that Yandex.Direct performed better in the selected niche and that the individual campaign planning for Yandex.Direct and Google AdWords is an important part of the optimization of search advertising in Russia.

Wind Turbine Direct-Drive Permanent-Magnet Generator with Direct Liquid Cooling for Mass Reduction

Today’s electrical machine technology allows increasing the wind turbine output power by an order of magnitude from the technology that existed only ten years ago. However, it is sometimes argued that high-power direct-drive wind turbine generators will prove to be of limited practical importance because of their relatively large size and weight. The limited space for the generator in a wind turbine application together with the growing use of wind energy pose a challenge for the design engineers who are trying to increase torque without making the generator larger. When it comes to high torque density, the limiting factor in every electrical machine is heat, and if the electrical machine parts exceed their maximum allowable continuous operating temperature, even for a short time, they can suffer permanent damage. Therefore, highly efficient thermal design or cooling methods is needed. One of the promising solutions to enhance heat transfer performances of high-power, low-speed electrical machines is the direct cooling of the windings. This doctoral dissertation proposes a rotor-surface-magnet synchronous generator with a fractional slot nonoverlapping stator winding made of hollow conductors, through which liquid coolant can be passed directly during the application of current in order to increase the convective heat transfer capabilities and reduce the generator mass. This doctoral dissertation focuses on the electromagnetic design of a liquid-cooled direct-drive permanent-magnet synchronous generator (LC DD-PMSG) for a directdrive wind turbine application. The analytical calculation of the magnetic field distribution is carried out with the ambition of fast and accurate predicting of the main dimensions of the machine and especially the thickness of the permanent magnets; the generator electromagnetic parameters as well as the design optimization. The focus is on the generator design with a fractional slot non-overlapping winding placed into open stator slots. This is an a priori selection to guarantee easy manufacturing of the LC winding. A thermal analysis of the LC DD-PMSG based on a lumped parameter thermal model takes place with the ambition of evaluating the generator thermal performance. The thermal model was adapted to take into account the uneven copper loss distribution resulting from the skin effect as well as the effect of temperature on the copper winding resistance and the thermophysical properties of the coolant. The developed lumpedparameter thermal model and the analytical calculation of the magnetic field distribution can both be integrated with the presented algorithm to optimize an LC DD-PMSG design. Based on an instrumented small prototype with liquid-cooled tooth-coils, the following targets have been achieved: experimental determination of the performance of the direct liquid cooling of the stator winding and validating the temperatures predicted by an analytical thermal model; proving the feasibility of manufacturing the liquid-cooled tooth-coil winding; moreover, demonstration of the objectives of the project to potential customers.

Modulation of Signaling Molecules by Human Leucocyte Antigen B27; Special Reference to STAT1

Reactive arthritis (ReA) is an inflammatory joint disease, which belongs to the group of Spondyloarthritis (SpA). It may occur after infections with certain gram-negative bacteria such as Salmonella and Yersinia. SpAs are strongly associated with the human leucocyte antigen (HLA)-B27. Despite active research, the mechanism by which HLA-B27 causes disease susceptibility is still unknown. However, HLA-B27 has a tendency to misfold during assembly. It is possible that the misfolding of HLA-B27 could alter signaling pathways and/or molecules involved in inflammatory response in cells. We have earlier discovered that in HLA-B27-positive cells the interaction between the host and causative bacteria is disturbed. Our recent studies indicate that the expression of HLA-B27 may alter certain signaling molecules by disturbing their activation. The aim of this study was to investigate whether the expression of HLA-B27 disturbs the signaling molecules, especially the phosphorylation of transcription factor STAT1. STAT1 is an important mediator of inflammatory responses. Our results show that the phosphorylation of the STAT1 is significantly altered in HLA-B27-expressing U937 monocytic cells compared with control cells. STAT1 tyrosine 701 is more strongly phosphorylated in HLAB27- expressing cells; whereas the phosphorylation of STAT1 serine 727 is prolonged. Phosphorylation of STAT1 was discovered to be dependent on protein kinase PKR. Furthermore, we found out that the expression of posttranscriptional gene regulator HuR was altered in HLA-B27-expressing cells. We also detected that HLA-B27-positive cells secrete more interleukin 6, which is an important mediator of inflammation. These results help to understand how HLA-B27 may confer susceptibility to SpAs.

Catalytic direct synthesis of hydrogen peroxide in a novel microstructured reactor

The direct synthesis from hydrogen and oxygen is a green alternative for production of hydrogen peroxide. However, this process suffers from two challenges. Firstly, mixtures of hydrogen and oxygen are explosive over a wide range of concentrations (4-94% H2 in O2). Secondly, the catalytic reaction of hydrogen and oxygen involves several reaction pathways, many of them resulting in water production and therfore decreasing selectivity. The present work deals with these two challenges. The safety problem was dealed by employing a novel microstructured reactor. Selectivity of the reaction was highly improved by development a set of new catalysts. The final goal was to develop an effective and safe continuous process for direct synthesis of hydrogen peroxide from H2 and O2. Activated carbon cloth and Sibunit were examined as the catalysts’ supports. Palladium and gold monometallic and palladium-gold bimetallic catalysts were thoroughly investigated by numerous kinetic experiments performed in a tailored batch reactor and several catalyst charachterization methods. A complete set of data for direct synthesis of H2O2 and its catalytic decomposition and hydrogenation was obtained. These data were used to assess factors influencing selectivity and activity of the catalysts in direct synthesis of H2O2 as well as its decomposition and hydrogenation. A novel microstructured reactor was developed based on hydrodynamics and mass transfer studies in prototype microstractural plates. The shape and the size of the structural elements in the microreactor plate were optimized in a way to get high gas-liquid interfacial area and gas-liquid mass transfer. Finally, empirical correlations for the volumetric mass transfer coefficient were derived. A bench-scale continuous process was developed by using the novel microstructral plate reactor. A series of kinetic experiments were performed to investigate the effects of the gas and the liquid feed rates and their ratio, the amount of the catalyst, the gas feed composition and pressure on the final rate of H2O2 production and selectivity.