Decentralized management of organic household wastes in the Kathmandu Valley using small-scale composting reactors

The sustainable management of municipal solid waste in the Kathmandu Valley has always been a challenging task. Solid waste generation has gone rapidly high in the Kathmandu Valley over the last decade due to booming population and rapid urbaniza-tion. Finding appropriate landfill sites for the disposal of solid wastes generated from the households of the Kathmandu Valley has always been a major problem for Nepalese government. 65 % of total generated wastes from the households of Nepal consist of organic materials. As large fractions of generated household wastes are organic in na-ture, composting can be considered as one of the best sustainable ways to recycle organ-ic wastes generated from the households of Nepal. Model Community Society Development (MCDS), a non-governmental organization of Nepal carried out its small-scale project in five households of the Kathmandu Valley by installing composting reactors. This thesis is based on this small-scale project and has used secondary data provided by MCDS Nepal for carrying out the study. Proper man-agement of organic wastes can be done at household levels through the use of compost-ing reactors. The end product compost can be used as soil conditioners for agricultural purposes such as organic farming, roof-top farming and gardening. The overall average organic waste generation in the Kathmandu Valley is found to be 0,23 kg/person/day and the total amount of organic household wastes generated in the Kathmandu Valley is around 210 Gg/yr. Produced composts from five composting reac-tors contain high amount of moistures but have sufficient amount of nutrients required for the fertility of land and plant growth. Installation of five composting reactors in five households have prevented 2,74 Mg of organic wastes going into the landfills, thus re-ducing 107 kg of methane emissions which is equivalent to 2,7 Mg of carbondioxide.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Deoxygenation of fatty acids for production of fuels and chemicals

The decreasing fossil fuel resources combined with an increasing world energy demand has raised an interest in renewable energy sources. The alternatives can be solar, wind and geothermal energies, but only biomass can be a substitute for the carbon–based feedstock, which is suitable for the production of transportation fuels and chemicals. However, a high oxygen content of the biomass creates challenges for the future chemical industry, forcing the development of new processes which allow a complete or selective oxygen removal without any significant carbon loss. Therefore, understanding and optimization of biomass deoxygenation processes are crucial for the future bio–based chemical industry. In this work, deoxygenation of fatty acids and their derivatives was studied over Pd/C and TiO2 supported noble metal catalysts (Pt, Pt–Re, Re and Ru) to obtain future fuel components. The 5 % Pd/C catalyst was investigated in semibatch and fixed bed reactors at 300 °C and 1.7–2 MPa of inert and hydrogen–containing atmospheres. Based on extensive kinetic studies, plausible reaction mechanisms and pathways were proposed. The influence of the unsaturation in the deoxygenation of model compounds and industrial feedstock – tall oil fatty acids – over a Pd/C catalyst was demonstrated. The optimization of the reaction conditions suppressed the formation of by–products, hence high yields and selectivities towards linear hydrocarbons and catalyst stability were achieved. Experiments in a fixed bed reactor filled with a 2 % Pd/C catalyst were performed with stearic acid as a model compound at different hydrogen–containing gas atmospheres to understand the catalyst stability under various conditions. Moreover, prolonged experiments were carried out with concentrated model compounds to reveal the catalyst deactivation. New materials were proposed for the selective deoxygenation process at lower temperatures (~200 °C) with a tunable selectivity to hydrodeoxygenation by using 4 % Pt/TiO2 or decarboxylation/decarbonylation over 4 % Ru/TiO2 catalysts. A new method for selective hydrogenation of fatty acids to fatty alcohols was demonstrated with a 4 % Re/TiO2 catalyst. A reaction pathway and mechanism for TiO2 supported metal catalysts was proposed and an optimization of the process conditions led to an increase in the formation of the desired products.

Loistehon säätö ja kompensointi

Kantaverkkoyhtiö Fingrid Oy on tarkastellut kantaverkosta otettua tai tuotettua loistehoa alueittain Fingridin määrittelemällä maantieteellisellä tavalla. Alue koostuu liittymispisteistä, jotka ovat yksittäisten verkkoyhtiöiden liittymispisteitä. Yhden alueen sisällä voi siis olla monia eri verkkoyhtiöiden liittymispisteitä. Vuodesta 2016 alkaen loistehon tarkastelu vaihtuu aluetarkastelusta liittymispistetarkasteluun. Liittymispistetarkasteluun siirtymisen myötä tulee verkkoyhtiöiden investoida erinäisiin kompensointiratkaisuihin, jotta yksittäisten liittymispisteiden loistehot pysyvät Fingridin asettaman loistehon tarkasteluikkunan sisällä. Työssä perehdytään erinäisiin kompensointiratkaisuihin ja niiden kytkentöihin sekä kytkentöjen vaikutuksiin olemassa olevaan sähköverkkoon. Lisäksi työssä käsitellään tuulivoimaloiden hyödyntämistä loistehon säädössä. Esimerkkitapauksessa tarkastellaan erästä Caruna Oy:n verkkoa ja pohditaan teknistä ja mahdollisimman taloudellista kompensointiratkaisua kyseiseen verkkoon. Työn lopputulos on, että maakaapeloinnin määrän kasvaessa loistehon kompensoinnin tarve kasvaa. Näin ollen Fingrid Oy:ltä tarvitaan selkeitä linjauksia moneen ongelmakohtaan, kuten tuotanto-kulutuspisteen loistehon tarkasteluun. Lisäksi Energiavirastolta tarvitaan kannusteita loistehon kompensointiin, sillä verkkoyhtiöiden liiketoiminta perustuu regulaatiomalliin ja kompensointilaitteiston yksikköhinnasto on hyvin suppea.

Prosessiautomaatio pinnankorkeusmittauksen koelaitteistoissa

Pinnankorkeuden tunteminen kiehutusvesireaktorin painesäiliössä on erittäin tärkeää sen turvallisuusvaikutusten takia. Pinnankorkeutta mitataan vesipatsaiden korkeutta havaitsevien paine-eromittausten avulla. Säteilyturvakeskuksen YVL-ohjeiden mukaan turvallisuuteen vaikuttavien mittausten täytyy noudattaa moninkertaistus- ja erilaisuusperiaatteita. Yleensä erilaisuusperiaatetta on toteutettu käyttämällä erityyppisiä paine-eromittareita, mutta erilaisella fysikaalisella toimintaperiaatteella oleva mittaus olisi parempi ja toteuttaisi paremmin erilaisuusperiaatetta. Uimurikytkin olisi tällainen fysikaalisesti eri periaatteeseen perustuva pinnankorkeuden mittauslaite. Ydinvoimalaan tarkoitettu teknologia tulee kelpoistaa riippumattoman tahon toimesta ennen käyttöönottoa. Kelpoistamiskokeita varten Lappeenrannan teknillisen yliopiston Ydinturvallisuuden tutkimusyksikköön rakennettiin vuosina 2011–2013 kaksi koelaitteistoa. Näillä koelaitteistoilla tutkittiin uimurikytkimien toimintaa ja ominaisuuksia erilaisissa kiehutusvesireaktorin käyttötilanteissa. Koelaitteistot tarvitsivat toimiakseen automaatiojärjestelmät, jotka suunniteltiin pääosin noudattamalla suunnittelun elinkaarimallia sekä automaatiosuunnittelun sisältökokonaisuuksia. Automaatiojärjestelmien suunnittelu aloitettiin määrittelemällä koejärjestelyjen asettamat vaatimukset, jonka jälkeen tehtiin teknologiavalinnat. Seuraavaksi suunniteltiin automaatiojärjestelmien logiikkaohjelmistot, joiden kuvaukseen tämä työ pääasiassa keskittyy. Logiikkaohjelmistot toteutettiin graafisella National Instruments LabView -ohjelmointikielellä. Logiikkaohjelmistojen tuli hoitaa tiedonkeruuta, käyttöautomaatiota, turvallisuustehtäviä sekä kokeisiin liittyviä erikoistehtäviä. Ohjelmistot saatiin esikokeiden aikana toimimaan halutusti, ja varsinaiset kokeet voitiin suorittaa ilman merkittäviä ongelmia.

Application and development of numerical methods for the modelling of innovative gas cooled fission reactors

Innovative gas cooled reactors, such as the pebble bed reactor (PBR) and the gas cooled fast reactor (GFR) offer higher efficiency and new application areas for nuclear energy. Numerical methods were applied and developed to analyse the specific features of these reactor types with fully three dimensional calculation models. In the first part of this thesis, discrete element method (DEM) was used for a physically realistic modelling of the packing of fuel pebbles in PBR geometries and methods were developed for utilising the DEM results in subsequent reactor physics and thermal-hydraulics calculations. In the second part, the flow and heat transfer for a single gas cooled fuel rod of a GFR were investigated with computational fluid dynamics (CFD) methods. An in-house DEM implementation was validated and used for packing simulations, in which the effect of several parameters on the resulting average packing density was investigated. The restitution coefficient was found out to have the most significant effect. The results can be utilised in further work to obtain a pebble bed with a specific packing density. The packing structures of selected pebble beds were also analysed in detail and local variations in the packing density were observed, which should be taken into account especially in the reactor core thermal-hydraulic analyses. Two open source DEM codes were used to produce stochastic pebble bed configurations to add realism and improve the accuracy of criticality calculations performed with the Monte Carlo reactor physics code Serpent. Russian ASTRA criticality experiments were calculated. Pebble beds corresponding to the experimental specifications within measurement uncertainties were produced in DEM simulations and successfully exported into the subsequent reactor physics analysis. With the developed approach, two typical issues in Monte Carlo reactor physics calculations of pebble bed geometries were avoided. A novel method was developed and implemented as a MATLAB code to calculate porosities in the cells of a CFD calculation mesh constructed over a pebble bed obtained from DEM simulations. The code was further developed to distribute power and temperature data accurately between discrete based reactor physics and continuum based thermal-hydraulics models to enable coupled reactor core calculations. The developed method was also found useful for analysing sphere packings in general. CFD calculations were performed to investigate the pressure losses and heat transfer in three dimensional air cooled smooth and rib roughened rod geometries, housed inside a hexagonal flow channel representing a sub-channel of a single fuel rod of a GFR. The CFD geometry represented the test section of the L-STAR experimental facility at Karlsruhe Institute of Technology and the calculation results were compared to the corresponding experimental results. Knowledge was gained of the adequacy of various turbulence models and of the modelling requirements and issues related to the specific application. The obtained pressure loss results were in a relatively good agreement with the experimental data. Heat transfer in the smooth rod geometry was somewhat under predicted, which can partly be explained by unaccounted heat losses and uncertainties. In the rib roughened geometry heat transfer was severely under predicted by the used realisable k − epsilon turbulence model. An additional calculation with a v2 − f turbulence model showed significant improvement in the heat transfer results, which is most likely due to the better performance of the model in separated flow problems. Further investigations are suggested before using CFD to make conclusions of the heat transfer performance of rib roughened GFR fuel rod geometries. It is suggested that the viewpoints of numerical modelling are included in the planning of experiments to ease the challenging model construction and simulations and to avoid introducing additional sources of uncertainties. To facilitate the use of advanced calculation approaches, multi-physical aspects in experiments should also be considered and documented in a reasonable detail.

Heterogeneous mass transfer in fluidized beds by computational fluid dynamics

The main objective of this research is to estimate and characterize heterogeneous mass transfer coefficients in bench- and pilot-scale fluidized bed processes by the means of computational fluid dynamics (CFD). A further objective is to benchmark the heterogeneous mass transfer coefficients predicted by fine-grid Eulerian CFD simulations against empirical data presented in the scientific literature. First, a fine-grid two-dimensional Eulerian CFD model with a solid and gas phase has been designed. The model is applied for transient two-dimensional simulations of char combustion in small-scale bubbling and turbulent fluidized beds. The same approach is used to simulate a novel fluidized bed energy conversion process developed for the carbon capture, chemical looping combustion operated with a gaseous fuel. In order to analyze the results of the CFD simulations, two one-dimensional fluidized bed models have been formulated. The single-phase and bubble-emulsion models were applied to derive the average gas-bed and interphase mass transfer coefficients, respectively. In the analysis, the effects of various fluidized bed operation parameters, such as fluidization, velocity, particle and bubble diameter, reactor size, and chemical kinetics, on the heterogeneous mass transfer coefficients in the lower fluidized bed are evaluated extensively. The analysis shows that the fine-grid Eulerian CFD model can predict the heterogeneous mass transfer coefficients quantitatively with acceptable accuracy. Qualitatively, the CFD-based research of fluidized bed process revealed several new scientific results, such as parametrical relationships. The huge variance of seven orders of magnitude within the bed Sherwood numbers presented in the literature could be explained by the change of controlling mechanisms in the overall heterogeneous mass transfer process with the varied process conditions. The research opens new process-specific insights into the reactive fluidized bed processes, such as a strong mass transfer control over heterogeneous reaction rate, a dominance of interphase mass transfer in the fine-particle fluidized beds and a strong chemical kinetic dependence of the average gas-bed mass transfer. The obtained mass transfer coefficients can be applied in fluidized bed models used for various engineering design, reactor scale-up and process research tasks, and they consequently provide an enhanced prediction accuracy of the performance of fluidized bed processes.

Simulation of the Interaction Mean Free Path between Neutrons and TRISO Particles

The interaction mean free path between neutrons and TRISO particles is simulated using scripts written in MATLAB to solve the increasing error present with an increase in the packing factor in the reactor physics code Serpent. Their movement is tracked both in an unbounded and in a bounded space. Their track is calculated, depending on the program, linearly directly using the position vectors of the neutrons and the surface equations of all the fuel particles; by dividing the space in multiple subspaces, each of which contain a fraction of the total number of particles, and choosing the particles from those subspaces through which the neutron passes through; or by choosing the particles that lie within an infinite cylinder formed on the movement axis of the neutron. The estimate from the current analytical model, based on an exponential distribution, for the mean free path, utilized by Serpent, is used as a reference result. The results from the implicit model in Serpent imply a too long mean free path with high packing factors. The received results support this observation by producing, with a packing factor of 17 %, approximately 2.46 % shorter mean free path compared to the reference model. This is supported by the packing factor experienced by the neutron, the simulation of which resulted in a 17.29 % packing factor. It was also observed that the neutrons leaving from the surfaces of the fuel particles, in contrast to those starting inside the moderator, do not follow the exponential distribution. The current model, as it is, is thus not valid in the determination of the free path lengths of the neutrons.

Thermal reactions of the major hydrocarbon components of biomass gasification gas

Gasification of biomass is an efficient method process to produce liquid fuels, heat and electricity. It is interesting especially for the Nordic countries, where raw material for the processes is readily available. The thermal reactions of light hydrocarbons are a major challenge for industrial applications. At elevated temperatures, light hydrocarbons react spontaneously to form higher molecular weight compounds. In this thesis, this phenomenon was studied by literature survey, experimental work and modeling effort. The literature survey revealed that the change in tar composition is likely caused by the kinetic entropy. The role of the surface material is deemed to be an important factor in the reactivity of the system. The experimental results were in accordance with previous publications on the subject. The novelty of the experimental work lies in the used time interval for measurements combined with an industrially relevant temperature interval. The aspects which are covered in the modeling include screening of possible numerical approaches, testing of optimization methods and kinetic modelling. No significant numerical issues were observed, so the used calculation routines are adequate for the task. Evolutionary algorithms gave a better performance combined with better fit than the conventional iterative methods such as Simplex and Levenberg-Marquardt methods. Three models were fitted on experimental data. The LLNL model was used as a reference model to which two other models were compared. A compact model which included all the observed species was developed. The parameter estimation performed on that model gave slightly impaired fit to experimental data than LLNL model, but the difference was barely significant. The third tested model concentrated on the decomposition of hydrocarbons and included a theoretical description of the formation of carbon layer on the reactor walls. The fit to experimental data was extremely good. Based on the simulation results and literature findings, it is likely that the surface coverage of carbonaceous deposits is a major factor in thermal reactions.

VVER-440 Thermal Hydraulics as a Computer Code Validation Challenge

This thesis concentrates on the validation of a generic thermal hydraulic computer code TRACE under the challenges of the VVER-440 reactor type. The code capability to model the VVER-440 geometry and thermal hydraulic phenomena specific to this reactor design has been examined and demonstrated acceptable. The main challenge in VVER-440 thermal hydraulics appeared in the modelling of the horizontal steam generator. The major challenge here is not in the code physics or numerics but in the formulation of a representative nodalization structure. Another VVER-440 specialty, the hot leg loop seals, challenges the system codes functionally in general, but proved readily representable. Computer code models have to be validated against experiments to achieve confidence in code models. When new computer code is to be used for nuclear power plant safety analysis, it must first be validated against a large variety of different experiments. The validation process has to cover both the code itself and the code input. Uncertainties of different nature are identified in the different phases of the validation procedure and can even be quantified. This thesis presents a novel approach to the input model validation and uncertainty evaluation in the different stages of the computer code validation procedure. This thesis also demonstrates that in the safety analysis, there are inevitably significant uncertainties that are not statistically quantifiable; they need to be and can be addressed by other, less simplistic means, ultimately relying on the competence of the analysts and the capability of the community to support the experimental verification of analytical assumptions. This method completes essentially the commonly used uncertainty assessment methods, which are usually conducted using only statistical methods.

Typenpoiston tehostaminen kunnallisessa jätevedenpuhdistuksessa membraanibioreaktorin avulla

Tämä diplomityö tehtiin Vihdin Vesihuoltolaitoksen Nummelan jäteveden puhdistamolle. Työssä tutkittiin typenpoistoa kunnallisista jätevesistä membraanibioreaktorin (MBR) avulla. MBR:ssä yhdistyvät perinteinen aktiivilieteprosessi ja kalvosuodatus. Työn tavoite oli päästä yli 95 % typenpoistoon. Aluksi typenpoisto oli yli 80 %, kun pilot-mittakaavan MBR-laitosta operoitiin perinteisen prosessin parametrein. Typenpoistoa onnistuttiin tehostamaan nostamalla nitraattipitoisen palautuslietteen kierrätystä prosessin alkupäähän (1600 L/h) ja lisäämällä aktiivista biomassaa reaktorissa. Yli 90 % typenpoisto edellytti myös pidempää viipymäaikaa (noin kaksinkertainen perinteiseen prosessiin verrattuna). Tutkimuksessa päästiin parhaimmillaan jopa 95 % typenpoistumaan operoimalla laitteistoa pienellä typpikuormalla (0,1 kg/vrk) ja alhaisemmalla lietepitoisuudella (10 g/L). Typpikuorman noustessa (0,3 kg/vrk) typenpoistoteho laski. Tätä onnistuttiin parantamaan (yli 90 %) nostamalla biomassan määrää reaktorissa (15 g/L). Hyvän typenpoiston saavuttaminen edellytti myös suurempaa metanolin ja hapen syöttöä.

Kullan talteenotto takaisinuuttoliuoksista

Työssä tutkittiin kirjallisuuden ja laboratoriomittausten avulla vaihtoehtoja kullan pelkistämiseen ja talteenottoon kultauuton takaisinuuttoliuoksista. Tavoitteena oli löytää menetelmä, jolla saadaan puhdasta kiinteää lopputuotetta ilman kullan häviöitä. Käytettyjä pelkistimiä olivat D-(+)-glukoosi, natriumboorihydridi, L-askorbiinihappo, D-(-)-isoaskorbiinihappo ja aktiivihiili. Laboratoriokokeiden perusteella D-(-)-isoaskorbiinihappo sekä aktiivihiili olivat sopivimmat pelkistimet kokeissa käytetylle kultaliuokselle. Isoaskorbiinihapolla suoritettiin panoskokeita lasireaktorissa eri alku-pH:ssa sekä erilaisilla pelkistimen ja kullan moolisuhteilla. Tulosten perusteella havaittiin pH:n ja pelkistimen ylimäärän vaikuttavan merkittävästi lopputuotteen puhtauteen. Myös redox-potentiaalia säätämällä ja happopesulla pelkistyksen jälkeen voidaan vaikuttaa lopputuotteen puhtauteen. Aktiivihiilellä suoritettiin panoskokeita adsorptiotasapainojen (latausisotermi) ja kinetiikan tutkimiseksi. Hiileen on mahdollista saada kultaa 383 mg/g kuivaa hiiltä. Suurempi lataus voitaisiin saavuttaa käyttämällä hiiltä, jolla on pienempi partikkelikoko. Kolonnikokeita tehtiin eri virtausnopeuksilla. Kolonnikokeissa kullan dynaaminen adsorptiokapasiteetti hiileen odotetusti kasvoi virtausnopeuden laskiessa. Pienin käytetty virtausnopeus oli 2,40 BV/h, jolloin kapasiteetti oli 75,4 mg/g kuivaa hiiltä (c (Au feed) = 129 mg/L). Kullasta voidaan poistaa myös kolonnipelkistyksen jälkeen epäpuhtauksia happopesulla. Isoaskorbiinihapolla pelkistyksen kinetiikka on nopea ja sillä saatiin pelkistettyä puhdasta lopputuotetta. Sekä isoaskorbiinihappo, että aktiivihiili ovat potentiaalisia menetelmiä kullan talteenottoon.

Two-phase flow measurements with spacer grid in a rod bundle geometry

Heat transfer effectiveness in nuclear rod bundles is of great importance to nuclear reactor safety and economics. An important design parameter is the Critical Heat Flux (CHF), which limits the transferred heat from the fuel to the coolant. The CHF is determined by flow behaviour, especially the turbulence created inside the fuel rod bundle. Adiabatic experiments can be used to characterize the flow behaviour separately from the heat transfer phenomena in diabatic flow. To enhance the turbulence, mixing vanes are attached to spacer grids, which hold the rods in place. The vanes either make the flow swirl around a single sub-channel or induce cross-mixing between adjacent sub-channels. In adiabatic two-phase conditions an important phenomenon that can be investigated is the effect of the spacer on canceling the lift force, which collects the small bubbles to the rod surfaces leading to decreased CHF in diabatic conditions and thus limits the reactor power. Computational Fluid Dynamics (CFD) can be used to simulate the flow numerically and to test how different spacer configurations affect the flow. Experimental data is needed to validate and verify the used CFD models. Especially the modeling of turbulence is challenging even for single-phase flow inside the complex sub-channel geometry. In two-phase flow other factors such as bubble dynamics further complicate the modeling. To investigate the spacer grid effect on two-phase flow, and to provide further experimental data for CFD validation, a series of experiments was run on an adiabatic sub-channel flow loop using a duct-type spacer grid with different configurations. Utilizing the wire-mesh sensor technology, the facility gives high resolution experimental data in both time and space. The experimental results indicate that the duct-type spacer grid is less effective in canceling the lift force effect than the egg-crate type spacer tested earlier.

Analysis and modelling of chemical looping combustion process with and without oxygen uncoupling

Effective control and limiting of carbon dioxide (CO₂) emissions in energy production are major challenges of science today. Current research activities include the development of new low-cost carbon capture technologies, and among the proposed concepts, chemical combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) have attracted significant attention allowing intrinsic separation of pure CO₂ from a hydrocarbon fuel combustion process with a comparatively small energy penalty. Both CLC and CLOU utilize the well-established fluidized bed technology, but several technical challenges need to be overcome in order to commercialize the processes. Therefore, development of proper modelling and simulation tools is essential for the design, optimization, and scale-up of chemical looping-based combustion systems. The main objective of this work was to analyze the technological feasibility of CLC and CLOU processes at different scales using a computational modelling approach. A onedimensional fluidized bed model frame was constructed and applied for simulations of CLC and CLOU systems consisting of interconnected fluidized bed reactors. The model is based on the conservation of mass and energy, and semi-empirical correlations are used to describe the hydrodynamics, chemical reactions, and transfer of heat in the reactors. Another objective was to evaluate the viability of chemical looping-based energy production, and a flow sheet model representing a CLC-integrated steam power plant was developed. The 1D model frame was succesfully validated based on the operation of a 150 kWth laboratory-sized CLC unit fed by methane. By following certain scale-up criteria, a conceptual design for a CLC reactor system at a pre-commercial scale of 100 MWth was created, after which the validated model was used to predict the performance of the system. As a result, further understanding of the parameters affecting the operation of a large-scale CLC process was acquired, which will be useful for the practical design work in the future. The integration of the reactor system and steam turbine cycle for power production was studied resulting in a suggested plant layout including a CLC boiler system, a simple heat recovery setup, and an integrated steam cycle with a three pressure level steam turbine. Possible operational regions of a CLOU reactor system fed by bituminous coal were determined via mass, energy, and exergy balance analysis. Finally, the 1D fluidized bed model was modified suitable for CLOU, and the performance of a hypothetical 500 MWth CLOU fuel reactor was evaluated by extensive case simulations.

Advanced analysis and design methods for preparative chromatographic separation processes

Preparative liquid chromatography is one of the most selective separation techniques in the fine chemical, pharmaceutical, and food industries. Several process concepts have been developed and applied for improving the performance of classical batch chromatography. The most powerful approaches include various single-column recycling schemes, counter-current and cross-current multi-column setups, and hybrid processes where chromatography is coupled with other unit operations such as crystallization, chemical reactor, and/or solvent removal unit. To fully utilize the potential of stand-alone and integrated chromatographic processes, efficient methods for selecting the best process alternative as well as optimal operating conditions are needed. In this thesis, a unified method is developed for analysis and design of the following singlecolumn fixed bed processes and corresponding cross-current schemes: (1) batch chromatography, (2) batch chromatography with an integrated solvent removal unit, (3) mixed-recycle steady state recycling chromatography (SSR), and (4) mixed-recycle steady state recycling chromatography with solvent removal from fresh feed, recycle fraction, or column feed (SSR–SR). The method is based on the equilibrium theory of chromatography with an assumption of negligible mass transfer resistance and axial dispersion. The design criteria are given in general, dimensionless form that is formally analogous to that applied widely in the so called triangle theory of counter-current multi-column chromatography. Analytical design equations are derived for binary systems that follow competitive Langmuir adsorption isotherm model. For this purpose, the existing analytic solution of the ideal model of chromatography for binary Langmuir mixtures is completed by deriving missing explicit equations for the height and location of the pure first component shock in the case of a small feed pulse. It is thus shown that the entire chromatographic cycle at the column outlet can be expressed in closed-form. The developed design method allows predicting the feasible range of operating parameters that lead to desired product purities. It can be applied for the calculation of first estimates of optimal operating conditions, the analysis of process robustness, and the early-stage evaluation of different process alternatives. The design method is utilized to analyse the possibility to enhance the performance of conventional SSR chromatography by integrating it with a solvent removal unit. It is shown that the amount of fresh feed processed during a chromatographic cycle and thus the productivity of SSR process can be improved by removing solvent. The maximum solvent removal capacity depends on the location of the solvent removal unit and the physical solvent removal constraints, such as solubility, viscosity, and/or osmotic pressure limits. Usually, the most flexible option is to remove solvent from the column feed. Applicability of the equilibrium design for real, non-ideal separation problems is evaluated by means of numerical simulations. Due to assumption of infinite column efficiency, the developed design method is most applicable for high performance systems where thermodynamic effects are predominant, while significant deviations are observed under highly non-ideal conditions. The findings based on the equilibrium theory are applied to develop a shortcut approach for the design of chromatographic separation processes under strongly non-ideal conditions with significant dispersive effects. The method is based on a simple procedure applied to a single conventional chromatogram. Applicability of the approach for the design of batch and counter-current simulated moving bed processes is evaluated with case studies. It is shown that the shortcut approach works the better the higher the column efficiency and the lower the purity constraints are.