Coolant Flow and Heat Transfer in Pebble-Bed Reactor Core

This thesis gathers knowledge about ongoing high-temperature reactor projects around the world. Methods for calculating coolant flow and heat transfer inside a pebble-bed reactor core are also developed. The thesis begins with the introduction of high-temperature reactors including the current state of the technology. Process heat applications that could use the heat from a high-temperature reactor are also introduced. A suitable reactor design with data available in literature is selected for the calculation part of the thesis. Commercial computational fluid dynamics software Fluent is used for the calculations. The pebble-bed is approximated as a packed-bed, which causes sink terms to the momentum equations of the gas flowing through it. A position dependent value is used for the packing fraction. Two different models are used to calculate heat transfer. First a local thermal equilibrium is assumed between the gas and solid phases and a single energy equation is used. In the second approach, separate energy equations are used for the phases. Information about steady state flow behavior, pressure loss, and temperature distribution in the core is obtained as results of the calculations. The effect of inlet mass flow rate to pressure loss is also investigated. Data found in literature and the results correspond each other quite well, considered the amount of simplifications in the calculations. The models developed in this thesis can be used to solve coolant flow and heat transfer in a pebble-bed reactor, although additional development and model validation is needed for better accuracy and reliability.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Role of Membrane Transporters, P-Glycoprotein and Mrp1, in The Placental Transfer of Drugs With Special Reference to Saquinavir and Quetiapine

Drug transporting membrane proteins are expressed in various human tissues and blood-tissue barriers, regulating the transfer of drugs, toxins and endogenous compounds into or out of the cells. Various in vitro and animal experiments suggest that P-glycoprotein (P-gp) forms a functional barrier between maternal and fetal blood circulation in the placenta thereby protecting the fetus from exposure to xenobiotics during pregnancy. The multidrug resistance-associated protein 1 (MRP1) is a relatively less studied transporter protein in the human placenta. The aim of this study series was to study the role of placental transporters, apical P-gp and basal MRP1, using saquinavir as a probe drug, and to study transfer of quetiapine and the role of P-gp in its transfer in the dually perfused human placenta/cotyledon. Furthermore, two ABCB1 (encoding P-gp) polymorphisms (c.3435C>T, p.Ile1145Ile and c.2677G>T/A, p.Ala893Ser/Thr) were studied to determine their impact on P-gp protein expression level and on the transfer of the study drugs. Also, the influence of the P-gp protein expression level on the transfer of the study drugs was addressed. Because P-gp and MRP1 are ATP-dependent drug-efflux pumps, it was studied whether exogenous ATP is needed for the function of ATP-dependent transporter in the present experimental model. The present results indicated that the addition of exogenous ATP was not necessary for transporter function in the perfused human placental cotyledon. Saquinavir and quetiapine were both found to cross the human placenta; transplacental transfer (TPTAUC %) for saquinavir was <0.5% and for quetiapine 3.7%. Pharmacologic blocking of P-gp led to disruption of the blood-placental barrier (BPB) and increased the placental transfer of P-gp substrate, saquinavir, into the fetal circulation by 6- to 8-fold. In reversed perfusions P-gp, MRP1 and possibly OATP2B1 had a negligible role in the fetal-to-maternal transfer of saquinavir. The TPTAUC % of saquinavir was about 100-fold greater from the fetal side to the maternal side compared with the maternal-to-fetal transfer. P-gp activity is not likely to modify the placental transfer of quetiapine. Higher P-gp protein expression levels were associated with the variant allele 3435T, but no correlation was found between the TPTAUC % of saquinavir and placental P-gp protein expression. The present results indicate that P-gp activity drastically affects the fetal exposure to saquinavir, and suggest that pharmacological blockade of the P-gp activity during pregnancy may pose an increased risk for adverse fetal outcome. The blockade of P-gp activity could be used in purpose to obtain higher drug concentration to the fetal side, for example, in prevention (to decrease virus transfer to fetal side) or in treating sick fetus.

Nanoparticle Labels in Bioaffinity Assays

Nanoparticles offer adjustable and expandable reactive surface area compared to the more traditional solid phase forms utilized in bioaffinity assays due to the high surface to-volume ratio. The versatility of nanoparticles is further improved by the ability to incorporate various molecular complexes such as luminophores into the core. Nanoparticle labels composed of polystyrene, silica, inorganic crystals doped with high number of luminophores, preferably lanthanide(III) complexes, are employed in bioaffinity assays. Other label species such as semiconductor crystals (quantum dots) or colloidal gold clusters are also utilized. The surface derivatization of such particles with biomolecules is crucial for the applicability to bioaffinity assays. The effectiveness of a coating is reliant on the biomolecule and particle surface characteristics and the selected coupling technique. The most critical aspects of the particle labels in bioaffinity assays are their size-dependent features. For polystyrene, silica and inorganic phosphor particles, these include the kinetics, specific activity and colloidal stability. For quantum dots and gold colloids, the spectral properties are also dependent on particle size. This study reports the utilization of europium(III)-chelate-embedded nanoparticle labels in the development of bioaffinity assays. The experimental covers both the heterogeneous and homogeneous assay formats elucidating the wide applicability of the nanoparticles. It was revealed that the employment of europium(III) nanoparticles in heterogeneous assays for viral antigens, adenovirus hexon and hepatitis B surface antigen (HBsAg), resulted in sensitivity improvement of 10-1000 fold compared to the reference methods. This improvement was attributed to the extreme specific activity and enhanced monovalent affinity of the nanoparticles conjugates. The applicability of europium(III)-chelate-doped nanoparticles to homogeneous assay formats were proved in two completely different experimental settings; assays based on immunological recognition or proteolytic activity. It was shown that in addition to small molecule acceptors, particulate acceptors may also be employed due to the high specific activity of the particles promoting proximity-induced reabsorptive energy transfer in addition to non-radiative energy transfer. The principle of proteolytic activity assay relied on a novel dual-step FRET concept, wherein the streptavidin-derivatized europium(III)-chelate-doped nanoparticles were used as donors for peptide substrates modified with biotin and terminal europium emission compliant primary acceptor and a secondary quencher acceptor. The recorded sensitized emission was proportional to the enzyme activity, and the assay response to various inhibitor doses was in agreement with those found in literature showing the feasibility of the technique. Experiments regarding the impact of donor particle size on the extent of direct donor fluorescence and reabsorptive excitation interference in a FRET-based application was conducted with differently sized europium(III)-chelate-doped nanoparticles. It was shown that the size effect was minimal

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Cost Optimisation of Mobile Advertising Client Data Transfer

Data traffic caused by mobile advertising client software when it is communicating with the network server can be a pain point for many application developers who are considering advertising-funded application distribution, since the cost of the data transfer might scare their users away from using the applications. For the thesis project, a simulation environment was built to mimic the real client-server solution for measuring the data transfer over varying types of connections with different usage scenarios. For optimising data transfer, a few general-purpose compressors and XML-specific compressors were tried for compressing the XML data, and a few protocol optimisations were implemented. For optimising the cost, cache usage was improved and pre-loading was enhanced to use free connections to load the data. The data traffic structure and the various optimisations were analysed, and it was found that the cache usage and pre-loading should be enhanced and that the protocol should be changed, with report aggregation and compression using WBXML or gzip.

Heat Transfer in Plate Heat Exchangers

This study illustrates the different types of plate heat exchangers that are commonly used in various domestic and industrial applications. The main purpose of this paper was to devise a methodology that is capable of calculating optimum number of plates in the design of a plate heat exchanger. To obtain the appropriate number of plates, typically several iterations must be made before a final acceptable design is completed, since plate amount depends on many factors such as, flow velocities, physical properties of the streams, flow channel geometry, allowable pressure drop, plate dimensions, and the gap between the plates. The methodology presented here can be used as a general guide for designing a plate heat exchanger. To investigate the effects of relevant parameters on the thermal-hydraulic design of a plate heat exchanger, several experiments were carried out for single-phase and counter flow arrangement with two brazed plate heat exchangers by varying the flow rates and the inlet temperatures of the fluid streams. The actual heat transfer coefficients obtained based on the experiment were nearly close to the calculated values and to improve the design, a correction factor was introduced. Besides, the effect of flow channel velocity on the pressure drop inside the unit is presented.

Sustainability of palm oil production and opportunities for Finnish technology and know-how transfer

The global demand for palm oil is growing, thus prompting an increase in the global production particularly in Malaysia and Indonesia. Such increasing demand for palm oil is due to palm oil’s relatively cheap price and versatile advantage both in edible and non-edible applications. Along with the increasing demand for palm oil, particularly for the production of biofuel, is a heated debate on its sustainability. Ecological degradation, climate change and social issues are among the main sustainability issues pressing the whole palm oil industry today. Clean Development Mechanism (CDM) projects fulfilling the imperatives of the Kyoto Protocol are starting to gain momentum in Malaysia as reflected by the increasing registration of CDM projects in the palm oil mills. Most CDM projects in palm oil mills are on waste-to-energy, cocomposting, and methane recovery with the latter being the most common. The study on greenhouse gases (GHG) in the milling process points that biogas collection and energy utilisation has the greatest positive effect on GHG balance. On the other hand, empty fruit bunches (EFB) end-use as energy and high energy efficiency of the mill have the least effect on GHG balance of the mill. The range of direct GHG emissions from the palm oil mill is from 2.5 to 27 gCO2e/MJCPO, while the range of GHG emissions with all indirect and avoided emissions included is from -9 to 29 gCO2e/MJCPO. Comparing this GHG balance result with that of the EU RES-Directive suggests a further check on the values and emissions consideration of the latter.

Heat transfer in superheaters of the bubbling fluidized bed boiler conversions

It is often reasonable to convert old boiler to bubbling fluidized bed boiler instead of building a new one. Converted boiler consists of old and new heat surfaces which must be fitted to operate together. Prediction of heat transfer in not so ideal conditions sets challenges for designers. Two converted boilers situated in Poland were studied on the grounds of acceptance tests and further studies. Calculation of boiler process was performed with boiler design program. Main interest was heat transfer in superheaters and factors affecting it. Theory for heat transfer is presented according to information found from literature. Results obtained from experimental studies and calculations have been compared. With correct definitions calculated parameters corresponded well to measured data at boiler maximum design load. However overload situations revealed to be difficult to model at least without considering changes in the combustion process which requires readjustments to the design program input values.

Lanthanide Chelates as Donors in Fluorescence Resonance Energy Transfer: Exciting Prospects for Bioaffinity Assay Detection

Fluorescence resonance energy transfer (FRET) is a non-radiative energy transfer from a fluorescent donor molecule to an appropriate acceptor molecule and a commonly used technique to develop homogeneous assays. If the emission spectrum of the donor overlaps with the excitation spectrum of the acceptor, FRET might occur. As a consequence, the emission of the donor is decreased and the emission of the acceptor (if fluorescent) increased. Furthermore, the distance between the donor and the acceptor needs to be short enough, commonly 10-100 Å. Typically, the close proximity between the donor and the acceptor is achieved via bioaffinity interactions e.g. antibody binding antigen. Large variety of donors and acceptors exist. The selection of the donor/acceptor pair should be done not only based on the requirements of FRET but also the performance expectancies and the objectives of the application should be considered. In this study, the exceptional fluorescence properties of the lanthanide chelates were employed to develop two novel homogeneous immunoassays: a non-competitive hapten (estradiol) assay based on a single binder and a dual-parametric total and free PSA assay. In addition, the quenching efficiencies and energy transfer properties of various donor/acceptor pairs were studied. The applied donors were either europium(III) or terbium(III) chelates; whereas several organic dyes (both fluorescent and quenchers) acted as acceptors. First, it was shown that if the interaction between the donor/acceptor complexes is of high quality (e.g. biotin-streptavidin) the fluorescence of the europium(III) chelate could be quenched rather efficiently. Furthermore, the quenching based homogeneous non-competitive assay for estradiol had significantly better sensitivity (~67 times) than a corresponding homogeneous competitive assay using the same assay components. Second, if the acceptors were chosen to emit at the emission minima of the terbium(III) chelate, several acceptor emissions could be measured simultaneously without significant cross-talk from other acceptors. Based on these results, the appropriate acceptors were chosen for the dual-parameter assay. The developed homogeneous dual-parameter assay was able to measure both total and free PSA simultaneously using a simple mix and measure protocol. Correlation of this assay to a heterogeneous single parameter assay was excellent (above 0.99 for both) when spiked human plasma samples were used. However, due to the interference of the sample material, the obtained concentrations were slightly lower with the homogeneous than the heterogeneous assay, especially for the free PSA. To conclude, in this work two novel immunoassay principles were developed, which both are adaptable to other analytes. However, the hapten assay requires a rather good antibody with low dissociation rate and high affinity; whereas the dual-parameter assay principle is applicable whenever two immunometric complexes can form simultaneously, provided that the requirements of FRET are fulfilled.

A three dimensional study of heat transfer in a supercritical circulating fluidized bed combustor

From the boiler design point of view, it is imperative to know and understand the operation of the boiler. Since comprehensive measurement of a large furnace is impossible, the furnace can be modeled in order to study its behavior and phenomena. This requires the used model to be validated to correspond with the physical furnace behavior. In this thesis, a three dimensional furnace model is validated to match a bituminous coal utilizing, supercritical once-through circulating fluidized bed combustor based on measurement data. The validated model is used for analyzing the furnace heat transfer. Other heat transfer analysis methods are energy balance method based on tube surface temperature measurements and a method based on measured temperature difference between the tube crest and the fin. The latter method was developed in the thesis using Fluent-software. In the theory part, literature is reviewed and the fundamental aspects of circulating fluidized bed are discussed. These aspects are solid particle behavior in fluidization known as hydrodynamics, behavior of fuel and combustion and heat transfer. Fundamental aspects of modeling are also presented.

Role of culture in knowledge transfer and sharing - case ERP implementation

The main objective of this study was to examine how culture influences knowledge transfer and sharing within multicultural ERP project implementation in China. The main interest was to explain how national culture and knowledge are linked by understanding how culture influences knowledge transfer and sharing in a project organization. The other objective of this work was to discuss what Chinese cultural characteristic inhibit and en-hance knowledge sharing in ERP project. The perspective of this study was qualitative and the empirical material was collected from theme interviews among Stora Enso employees. Conclusion of this thesis is that Finns have a very direct style of communication and sharing knowledge whereas Chinese respect face shaving and indirect communication. Another conclusion is that knowledge sharing does not “just happen”, it is needed that project members understand national culture to get all project members commitment to project. In China most important is understand local business processes and understand role of trust and guanxi.

Leaf-Targeted Ferredoxin-NADP+-Oxidoreductase (FNR): Electron Transfer Properties and Thylakoid Association in Arabidopsis thaliana

Photosynthetic reactions are divided in two parts: light-driven electron transfer reactions and carbon fixation reactions. Electron transfer reactions capture solar energy and split water molecules to form reducing energy (NADPH) and energy-carrying molecules (ATP). These end-products are used for fixation of inorganic carbon dioxide into organic sugar molecules. Ferredoxin-NADP⁺ oxidoreductase (FNR) is an enzyme that acts at the branch point between the electron transfer reactions and reductive metabolism by catalyzing reduction of NADP+ at the last step of the electron transfer chain. In this thesis, two isoforms of FNR from A rabidopsis thaliana, FNR1 and FNR2, were characterized using the reverse genetics approach. The fnr1 and fnr2 mutant plants resembled each other in many respects. Downregulation of photosynthesis protected the single fnr mutant plants from excess formation of reactive oxygen species (ROS), even without significant upregulation of antioxidative mechanisms. Adverse growth conditions, however, resulted in phenotypic differences between fnr1 and fnr2. While fnr2 plants showed downregulation of photosynthetic complexes and upregulation of antioxidative mechanisms under low-temperature growth conditions, fnr1 plants had the wild-type phenotype, indicating that FNR2 may have a specific role in redistribution of electrons under unfavorable conditions. The heterozygotic double mutant (fnr1xfnr2) was severely devoid of chloroplastic FNR, which clearly restricted photosynthesis. The fnr1xfnr2 plants used several photoprotective mechanisms to avoid oxidative stress. In wild-type chloroplasts, both FNR isoforms were found from the stroma, the thylakoid membrane, and the inner envelope membrane. In the absence of the FNR1 isoform, FNR2 was found only in the stroma, suggesting that FNR1 and FNR2 form a dimer, by which FNR1 anchors FNR2 to the thylakoid membrane. Structural modeling predicted formation of an FNR dimer in complex with ferredoxin. In this thesis work, Tic62 was found to be the main protein that binds FNR to the thylakoid membrane, where Tic62 and FNR formed high molecular weight complexes. The formation of such complexes was shown to be regulated by the redox state of the chloroplast. The accumulation of Tic62-FNR complexes in darkness and dissociation of complexes from the membranes in light provide evidence that the complexes may have roles unrelated to photosynthesis. This and the high viability of fnr1 mutant plants lacking thylakoid-bound FNR indicate that the stromal pool of FNR is photosynthetically active.

External knowledge transfer mechanisms in service business acquisition

In knowledge-intensive economy an effective knowledge transfer is a part of the firm’s strategy to achieve a competitive advantage in the market. Knowledge transfer related to a variety of mechanisms depends on the nature of knowledge and context. The topic is, however, very little empirical studied and there is a research gap in scientific literature. This study examined and analyzed external knowledge transfer mechanisms in service business and especially in the context of acquisitions. The aim was to find out what kind of mechanisms was used when the buyer began to transfer data e.g. their own agendas and practices to the purchased units. Another major research goal was to identify the critical factors which contributed to knowledge transfer through different mechanisms. The study was conducted as a multiple-case study in a consultative service business company, in its four business units acquired by acquisition, in various parts of the country. The empirical part of the study was carried out as focus group interviews in each unit, and the data were analyzed using qualitative methods. The main findings of this study were firstly the nine different knowledge transfer mechanisms in service business acquisition: acquisition management team as an initiator, unit manager as a translator, formal training, self-directed learning, rooming-in, IT systems implementation, customer relationship management, codified database and ecommunication. The used mechanisms brought up several aspects as giving the face to changing, security of receiving right knowledge and correctly interpreted we-ness atmosphere, and orientation to use more consultative touch with customers. The study pointed out seven critical factors contributed to different mechanisms: absorption, motivation, organizational learning, social interaction, trust, interpretation and time resource. The two last mentioned were new findings compared to previous studies. Each of the mechanisms and the related critical factors contributed in different ways to the activity in different units after the acquisition. The role of knowledge management strategy was the most significant managerial contribution of the study. Phenomenon is not recognized enough although it is strongly linked in knowledge based companies. The recognition would help to develop a better understanding of the business through acquisitions, especially in situations such as where two different knowledge strategies combines in new common company.