Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

Suunnittelulla ja ruo´on hyötykäytöllä tehokkuutta rantojen hoitoon : Tuloksia ja kokemuksia VELHO-hankkeesta

Varsinais-Suomen ELY-keskuksen toteuttamassa VELHO-hankkeessa kehitettiin kustannustehokkaita ratkaisuja ranta-alueiden umpeenkasvun aiheuttamiin ongelmiin luomalla uusi konsepti ranta-alueiden monikäyttösuunnitteluun, edistämällä järviruo’on hyötykäyttöä ja valmistelemalla esityksiä uuteen maaseudun kehittämisohjelmaan. Tässä julkaisussa esitellään työn tulokset ja johtopäätökset. Hankkeessa laadittiin kolme ranta-alueiden monikäyttösuunnitelmaa: Mynälahden Sarsalanaukko ja Musta-aukko, Oukkulanlahti – Naantalinaukko ja Eurajoen - Luvian rannikko. Suunnitelmissa sovitettiin yhteen ranta-alueiden eri käyttömuotoja ja pyrittiin löytämään optimaalinen verkosto hyötykäyttöön leikattavien ruovikoiden, avoimena pidettävien merenrantaniittyjen ja säilytettävien ruovikoiden välille. Kustannustehokkuuteen pyrittiin kohdentamalla hoitotoimet laajoihin kokonaisuuksiin sekä järviruo’on hyötykäytöllä. Suunnitelmat laadittiin laajassa osallistavassa prosessissa. Hankkeessa laadituissa ranta-alueiden monikäyttösuunnitelmissa esitettiin erilaisia maankäyttötavoitteita ja hoitosuosituksia yli 2000 hehtaarille. Ruovikoiden ja rantaniittyjen lisäksi suunnittelun kohteena olivat myös rantojen läheiset peltoalueet, reunavyöhykkeet ja muut perinnebiotoopit. Hoitotoimilla tavoitellaan alueiden luonnon monimuotoisuuden ja vesien tilan paranemista, maiseman avartumista ja virkistyskäytön helpottumista. Ruovikoiden erilaisia leikkuumenetelmiä (talvileikkuut, vesileikkuut, maaleikkuut) testattiin 90 hehtaarin alalla. Rantaniittyjen kunnostuksessa testattiin maaleikkuun lisäksi ruovikon niittomurskausta. Ruokomassan hyötykäyttökokeissa testattiin kahden eri ruokolaadun eli tuoreen kesäruo’on ja kuivan talviruo’on esikäsittelyä ja hyötykäyttöä energiantuotannossa (poltto, biokaasutus) ja maataloudessa (maanparannusaine, viherlannoite, kuivike, katemateriaali). Maaseudun kehittämisohjelmaan tehtiin esityksiä tukimuotojen kehittämiseksi: rantaniittyjen kunnostuksen lisääminen ja hoidon laadun parantaminen, ruovikoiden vesileikkuut ravinteiden poistajina sekä ruokomassojen käyttö maan orgaanisen aineen lisääjänä. Hankkeen kokemusten mukaan yksi kustannustehokkaimmista hoito- ja käyttöketjuista on ruovikon leikkuu loppukesällä ja siitä kertyvän massan käyttö ranta-alueiden läheisillä pelloilla viherlannoitteena ja maanparannusaineena. Yhden hehtaarin ruovikon kesäleikkuulla poistetaan keskimäärin 80 kg typpeä ja 7 kg fosforia. Vesiensuojelullisten hyötyjen lisäksi leikkuulla parannetaan umpeenkasvusta kärsivien lajien elinoloja, lisätään rantojen vetovoimaisuutta ja edistetään luonnonhoitoyrittäjyyden edellytyksiä. Peltokäytössä käsittelyketju on lyhyt eikä se vaadi pitkiä kuljetusmatkoja. Ruokomassa kierrättää ravinteita takaisin pelloille ja parantaa maan rakennetta. Järviruo’on hyötykäytöllä ei pystytä kattamaan koko leikkuu- ja käyttöketjun kustannuksia. Leikkuusta ja hyötykäytöstä saatavien monien eri aineellisten ja aineettomien ekosysteemipalveluhyötyjen vuoksi toimintaan on tarpeen suunnata yhteiskunnan tukea ja luoda käytännön toteutusta edistäviä tukimuotoja. Kustannustehokkuutta voidaan edelleen parantaa laitteita ja menetelmiä kehittämällä.

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.

Development of an HTR-10 model in the Serpent reactor physics code

The use of exact coordinates of pebbles and fuel particles of pebble bed reactor modelling becoming possible in Monte Carlo reactor physics calculations is an important development step. This allows exact modelling of pebble bed reactors with realistic pebble beds without the placing of pebbles in regular lattices. In this study the multiplication coefficient of the HTR-10 pebble bed reactor is calculated with the Serpent reactor physics code and, using this multiplication coefficient, the amount of pebbles required for the critical load of the reactor. The multiplication coefficient is calculated using pebble beds produced with the discrete element method and three different material libraries in order to compare the results. The received results are lower than those from measured at the experimental reactor and somewhat lower than those gained with other codes in earlier studies.

Three-dimensional modeling of biomass fuel flow in a circulating fluidized bed furnace

The reduction of greenhouse gas emissions in the European Union promotes the combustion of biomass rather than fossil fuels in energy production. Circulating fluidized bed (CFB) combustion offers a simple, flexible and efficient way to utilize untreated biomass in a large scale. CFB furnaces are modeled in order to understand their operation better and to help in the design of new furnaces. Therefore, physically accurate models are needed to describe the heavily coupled multiphase flow, reactions and heat transfer inside the furnace. This thesis presents a new model for the fuel flow inside the CFB furnace, which acknowledges the physical properties of the fuel and the multiphase flow phenomena inside the furnace. This model is applied with special interest in the firing of untreated biomass. An experimental method is utilized to characterize gas-fuel drag force relations. This characteristic drag force approach is developed into a gas-fuel drag force model suitable for irregular, non-spherical biomass particles and applied together with the new fuel flow model in the modeling of a large-scale CFB furnace. The model results are physically valid and achieve very good correspondence with the measurement results from large-scale CFB furnace firing biomass. With the methods and models presented in this work, the fuel flow field inside a circulating fluidized bed furnace can be modeled with better accuracy and more efficiently than in previous studies with a three-dimensional holistic model frame.