Reaktorisydämen valvontajärjestelmän modernisointi Olkiluodon kiehutusvesilaitoksella

Reaktorisydämen valvonnalla varmistetaan, että polttoaineelta vaaditut termiset marginaalit toteutuvat ja polttoaineen suojakuori säilyy ehjänä. Olkiluodon kiehutusvesilaitoksen nykyinen sydämen valvontajärjestelmä koostuu SIMULATE-3-sydänsimulaattoriohjelmasta, reaktorisydämen instrumentoinnista, termisen tehon laskentaohjelmasta, tiedonkeruuohjelmista ja käynnistysautomatiikasta. Uusi järjestelmä koostuu näiden lisäksi GARDEL-ohjelmasta, joka on kehitetty kevytvesireaktoreiden sydämen käytön suunnitteluun ja valvontaan. GARDEL käyttää laskentaan samoja ohjelmia, jotka ovat jo Olkiluodon kiehutusvesilaitoksella käytössä. Tämän työn tarkoituksena oli verrata nykyistä ja uutta sydämen valvontajärjestelmää Olkiluodon kiehutusvesilaitoksella. Työssä tutkittiin LPRM-detektorien kalibroinnin jälkeisen datan käsittelyä, palamapäivitystä, stabiilisuuslaskentaa ja adaptiivisia menetelmiä. Järjestelmien vertailuun käytettiin Olkiluoto 2 -laitosyksiköltä käyttöjaksolta 31 (2011–2012) saatuja laskentuloksia. Tulosten perusteella havaittiin uuden järjestelmän laskennassa yksittäisiä virheitä, jotka tulee korjata. Lisäksi uuden järjestelmän toiminnasta tarvitaan lisäselvitystä.

Ydinvoimalaitosten vesikemia ja korroosionesto

Ydinvoimalaitosten vesikemian optimointi ja korroosionesto on välttämätöntä laitosten taloudellisen ja turvallisen käytön kannalta. Eri laitoksiin liittyvää vesikemiaa ja järjestelmissä havaittavia korroosion muotoja on tutkittu laajasti ja tutkitaan yhä edelleen. Monien prosessien ymmärtäminen vaatii usean eri tieteenalan osaamista, kuten kemiantekniikan, energiatekniikan sekä materiaalitekniikan. Tässä työssä kerrotaan yksinkertaistaen vesikemiaan ja korroosioon liittyviä prosesseja ja reaktioita. Työssä käsitellään kevytvettä jäähdytteenä sekä moderaattorina käyttävien ydinvoimalaitosten eri korroosiomuotoja sekä säteilyn vaikutusta näihin suoraan tai vesikemian kautta. Työssä kerrotaan korroosio- ja aktivoitumistuotteiden muodostumisesta ja kulkeutumisesta sekä näiden tuotteiden vaikutuksista laitosten toimintaan. Korroosion ja materiaalien aktivoitumisen pohjalta tarkastellaan kattavasti ydinvoimalaitosten tyypillisimpiä vesikemian muokkauskeinoja sekä korroosionhallintaa. Tärkeimpiin asioihin syvennytään hieman lähemmin. Tarkastelun kohteena ovat eniten käytetyt ydinvoimalaitokset, eli länsimaiset paine- ja kiehutusvesilaitokset sekä venäläisvalmisteiset VVER-laitokset. Tarkoituksena on ollut luoda tiivis tietopaketti opiskelijoiden käyttöön muun opintomateriaalin tueksi.

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.

Coolability of porous core debris beds : Effects of bed geometry and multi-dimensional flooding

This thesis addresses the coolability of porous debris beds in the context of severe accident management of nuclear power reactors. In a hypothetical severe accident at a Nordic-type boiling water reactor, the lower drywell of the containment is flooded, for the purpose of cooling the core melt discharged from the reactor pressure vessel in a water pool. The melt is fragmented and solidified in the pool, ultimately forming a porous debris bed that generates decay heat. The properties of the bed determine the limiting value for the heat flux that can be removed from the debris to the surrounding water without the risk of re-melting. The coolability of porous debris beds has been investigated experimentally by measuring the dryout power in electrically heated test beds that have different geometries. The geometries represent the debris bed shapes that may form in an accident scenario. The focus is especially on heap-like, realistic geometries which facilitate the multi-dimensional infiltration (flooding) of coolant into the bed. Spherical and irregular particles have been used to simulate the debris. The experiments have been modeled using 2D and 3D simulation codes applicable to fluid flow and heat transfer in porous media. Based on the experimental and simulation results, an interpretation of the dryout behavior in complex debris bed geometries is presented, and the validity of the codes and models for dryout predictions is evaluated. According to the experimental and simulation results, the coolability of the debris bed depends on both the flooding mode and the height of the bed. In the experiments, it was found that multi-dimensional flooding increases the dryout heat flux and coolability in a heap-shaped debris bed by 47–58% compared to the dryout heat flux of a classical, top-flooded bed of the same height. However, heap-like beds are higher than flat, top-flooded beds, which results in the formation of larger steam flux at the top of the bed. This counteracts the effect of the multi-dimensional flooding. Based on the measured dryout heat fluxes, the maximum height of a heap-like bed can only be about 1.5 times the height of a top-flooded, cylindrical bed in order to preserve the direct benefit from the multi-dimensional flooding. In addition, studies were conducted to evaluate the hydrodynamically representative effective particle diameter, which is applied in simulation models to describe debris beds that consist of irregular particles with considerable size variation. The results suggest that the effective diameter is small, closest to the mean diameter based on the number or length of particles.

Improvement of pyrolysis oil quality by scrubbing

Diplomityössä tutkittiin kuuman pyrolyysihöyryn puhdistamista haisevista ja kevyistä haihtuvista yhdisteistä. Työn kirjallisuusosassa selvitettiin pyrolyysiöljyn kannattavuutta uusiutuvana energialähteenä. Lisäksi eri pesurityyppejä tarkasteltiin ja ja vertailtiin. Työn kokeellisessa osassa käytettiin kahta erilaista koelaitteistoa. Tuotteen talteenotossa vertailtiin reaktorilämpötilan ja raaka-aineen kosteuden vaikutusta pyrolyysisaantoihin. Komponenttien talteenotossa tutkittiin epästabiilien ja pistävän hajuisten yhdisteiden poistamista kuumasta pyrolyysihöyrystä. Raaka-aineena käytettiin kuusen metsätäh-dehaketta, joka sisältää runsaasti neulasia ja kaarnaa. Kokeet toteutettiin lämpötila-alueella 460 - 520 °C. Koelaitteistot koostuivat kaasun (N2) syöttöjärjestelmään kytketystä kuumasta ja kyl-mästä puolesta. Tuotteen talteenotossa kuuma pyrolyysihöyry jäähdytettiin ja otettiin talteen. Komponenttien talteenotossa tuote kerättiin suodattimelle ja metyleeniklo-ridiloukkuun. Tuotteiden koostumukset analysoitiin kaasukromatokrafilla. Korkeimmat orgaaniset saannot saatiin 480 °C reaktorilämpötilalla ja 8-9 p-% raaka-ainekosteudella. Pyrolyysiveden määrä putosi raaka-aineen kosteutta nostettaessa. Eri reaktorilämpötiloilla ja raaka-ainekosteuksilla ei ollut vaikutusta hiiltosaantoihin. Kaasusaannot (pääosin CO2, CO ja hiilivedyt) olivat noin 10 p-%. Komponenttien talteenotossa suodatin tukkeutui matalissa (< 250 °C) lämpötiloissa. Suodattimelle jäänyt materiaali oli pääosin neulasista ja kaarnasta peräisin olevia uuteaineita (pääosin hartsi- rasvahappoja) ja sokereita. Korkeimmissa lämpötiloissa (> 250 °C) uuteaineet läpäisivät suodattimen paremmin. 250 ja 300 °C:n lämpötiloissa suuri määrä lyhytketjuisia helposti haihtuvia epästabiileja ja haisevia yhdisteitä (ketoneja, furaani- ja furfuraalijohdannaisia jne.) jäi metyleenikloridi- ja metanoliloukkuihin.

Nutrient enrichment and water depth modify consumer control in rocky shore macroalgal communities

The objective of my thesis is to assess mechanisms of ecological community control in macroalgal communities in the Baltic Sea. In the top-down model, predatory fish feed on invertebrate mesograzers, releasing algae partly from grazing pressure. Such a reciprocal relationship is called trophic cascade. In the bottom-up model, nutrients increase biomass in the food chain. The nutrients are first assimilated by algae and, via food chain, increase also abundance of grazers and predators. Previous studies on oceanic shores have described these two regulative mechanisms in the grazer - alga link, but how they interact in the trophic cascades from fish to algae is still inadequately known. Because the top-down and bottom-up mechanisms are predicted to depend on environmental disturbances, such as wave stress and light, I have studied these models at two distinct water depths. There are five factorial field experiments behind the thesis, which were all conducted in the Finnish Archipelago Sea. In all the experiments, I studied macroalgal colonization - either density, filament length or biomass - on submerged colonization substrates. By excluding predatory fish and mesograzers from the algal communities, the studies compared the strength of the top-down control to natural algal communities. A part of the experimental units were, in addition, exposed to enriched nitrogen and phosphorus concentrations, which enabled testing of bottom-up control. These two models of community control were further investigated in shallow (<1 m) and deep (ca. 3 m) water. Moreover, the control mechanisms were also expected to depend on grazer species. Therefore different grazer species were enclosed into experimental units and their impacts on macroalgal communities were followed specifically. The community control in the Baltic rocky shores was found to follow theoretical predictions, which have not been confirmed by field studies before. Predatory fish limited grazing impact, which was seen as denser algal communities and longer algal filaments. Nutrient enrichment increased density and filament length of annual algae and, thus, changed the species composition of the algal community. The perennial alga Fucus vesiculosusA and the red alga Ceramium tenuicorne suffered from the increased nutrient availabilities. The enriched nutrient conditions led to denser grazer fauna, thereby causing strong top-down control over both the annual and perennial macroalgae. The strength of the top-down control seemed to depend on the density and diversity of grazers and predators as well as on the species composition of macroalgal assemblages. The nutrient enrichment led to, however, weaker limiting impact of predatory fish on grazer fauna, because fish stocks did not respond as quickly to enhanced resources in the environment as the invertebrate fauna. According to environmental stress model, environmental disturbances weaken the top-down control. For example, on a wave-exposed shore, wave stress causes more stress to animals close to the surface than deeper on the shore. Mesograzers were efficient consumers at both the depths, while predation by fish was weaker in shallow water. Thus, the results supported the environmental stress model, which predicts that environmental disturbance affects stronger the higher a species is in the food chain. This thesis assessed the mechanisms of community control in three-level food chains and did not take into account higher predators. Such predators in the Baltic Sea are, for example, cormorant, seals, white-tailed sea eagle, cod and salmon. All these predatory species were recently or are currently under intensive fishing, hunting and persecution, and their stocks have only recently increased in the region. Therefore, it is possible that future densities of top predators may yet alter the strengths of the controlling mechanisms in the Baltic littoral zone.

High voltage discharge for degradation of organic contaminants in water

The pulsed dielectric barrier discharge (PDBD) and pulsed corona discharge (PCD) were compared for their efficiency to degrade phenol in water solution. Results show that PCD has higher efficiency than PDBD to degrade phenol. When initial pH of water solution was elevated, phenol degradation in the PCD reactor was significantly enhanced, although no considerable effect was seen in the PDBD reactor. The PCD reactor was also able to degrade lignin significantly, both in synthetically prepared solution and in pulp and paper mill wastewater. Water temperature did not affect phenol degradation; however, lignin was better oxidized at lower temperature.

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.

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.

Ultraviolet light protection and weathering properties of wood-polypropylene composites

The main aim of this thesis is to study the effect of pigments on the weathering properties of wood-polypropylene composites (WPC). The studied properties are color change, water absorption, thickness swelling and Charpy impact strength. The impact of weathering and UV exposure on WPCs was studied by using pigments and minerals as protective agents. The study shows that the pigments and/or mineral fillers can be used to improve the weathering properties of WPCs. The effect of pigments was found to vary with the type of pigment and the method of weathering. The black pigment, an inorganic carbon black master-batch, was found to be the most effective one in reduction of the discoloration of WPCs. By preventing discoloration, and further reducing the degradation of the surface of the WPC, the pigments were found to reduce the decrease in the impact strength after weathering. As well as UV protection, the moisture resistance is a significant factor affecting the durability of WPCs. The addition of mineral fillers was found to improve the moisture-related properties, such as water absorption and thickness swelling, of WPC significantly. According to the findings, addition of pigments and mineral fillers to wood-polypropylene composites appears to be beneficial: color stability and moisture resistance can be enhanced especially in outdoor weathering. The combined effect of black pigment (carbon black master-batch) and wollastonite as a mineral filler was found to bring about the most effective properties against weathering.

Modification of Photocatalyst with Enhanced Photocatalytic Activity for Water

Increasing demand and shortage of energy resources and clean water due to the rapid development of industry, population growth and long term droughts have become an issue worldwide. As a result, global warming, long term droughts and pollution-related diseases are becoming more and more serious. The traditional technologies, such as precipitation, neutralization, sedimentation, filtration and waste immobilization, cannot prevent the pollution but restrict the waste chemicals only after the pollution emission. Meanwhile, most of these treatments cannot thoroughly degrade the contaminants and may generate toxic secondary pollutants into ecosystem. Heterogeneous photocatalysis as the innovative wastewater technology attracts many attention, because it is able to generate highly reactive transitory species for total degradation of organic compounds, water pathogens and disinfection by-products. Semiconductor as photocatalysts have demonstrated their efficiency in degrading a wide range of organics into readily biodegradable compounds, and eventually mineralized them to innocuous carbon dioxide and water. But, the efficiency of photocatalysis is limited, and hence, it is crucial issue to modify photocatalyst to enhance photocatalytic activity. In this thesis, first of all, two literature views are conducted. A survey of materials for photocatalysis has been carried out in order to summarize the properties and the applications of photocatalysts that have been developed in this field. Meanwhile, the strategy for the improvement of photocatalytic activity have been explicit discussed. Furthermore, all the raw material and chemicals used in this work have been listed as well as a specific experimental process and characterization method has been described. The synthesize methods of different photocatalysts have been depicted step by step. Among these cases, different modification strategies have been used to enhance the efficiency of photocatalyst on degradation of organic compounds (Methylene Blue or Phenol). For each case, photocatalytic experiments have been done to exhibit their photocatalytic activity.The photocatalytic experiments have been designed and its process have been explained and illustrated in detailed. Moreover, the experimental results have been shown and discussion. All the findings have been demonstrated in detail and discussed case by case. Eventually, the mechanisms on the improvement of photocatalytic activities have been clarified by characterization of samples and analysis of results. As a conclusion, the photocatalytic activities of selected semiconductors have been successfully enhanced via choosing appropriate strategy for the modification of photocatalysts.

Spectral characteristics of bacteriorhodopsin water solution

The object of the study is bacteriorhodopsin. This light-sensitive protein have been selected as perspective substance for optical and optoelectronic applications. Bacteriorhodopsin carries out pumping protons through the cell membrane. Biomolecule converts light into an electric signal when sandwiched between electrodes. These properties were utilized in this research to implement photosensors on the basis of BR layers. These properties were utilized in this research to the bR water solution. According to the absorption spectra and using Kramers – Kronig relation the extinction coefficient has been calculated, as well as the related change of the refractive index value.

Geographical Studies of Underwater Light Dynamics in the Coastal Archipelago of SW Finland, Baltic Sea

The underwater light field is an important environmental variable as it, among other things, enables aquatic primary production. Although the portion of solar radiation that is referred to as visible light penetrates water, it is restricted to a limited surface water layer because of efficient absorption and scattering processes. Based on the varying content of optical constituents in the water, the efficiency of light attenuation changes in many dimensions and over various spatial and temporal scales. This thesis discusses the underwater light dynamics of a transitional coastal archipelago in south-western Finland, in the Baltic Sea. While the area has long been known to have a highly variable underwater light field, quantified knowledge on the phenomenon has been scarce, patchy, or non-existent. This thesis focuses on the variability in the underwater light field through euphotic depths (1% irradiance remaining), which were derived from in situ measurements of vertical profiles of photosynthetically active radiation (PAR). Spot samples were conducted in the archipelago of south-western Finland, mainly during the ice-free growing seasons of 2010 and 2011. In addition to quantifying both the seasonal and geographical patterns of euphotic depth development, the need and usability of underwater light information are also discussed. Light availability was found to fluctuate in multiple dimensions and scales. The euphotic depth was shown to have combined spatio-temporal dynamics rather than separate changes in spatial and temporal dimensions. Such complexity in the underwater light field creates challenges in data collection, as well as in its utilisation. Although local information is needed, in highly variable conditions spot sampled information may only poorly represent its surroundings. Moreover, either temporally or spatially limited sampling may cause biases in understanding underwater light dynamics. Consequently, the application of light availability data, for example in ecological modelling, should be made with great caution.

A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

Solutions to water problems in the bottom of the pyramid market

Solving the water crisis in the developing world is a critical issue. Four billion people in the globe, so called the Base of the Pyramid (BoP) population suffer from inadequate access to safe drinking water, while millions die daily from waterborne diseases and lack of clean water. The BoP people desperately need to obtain a satisfactory access to safe water sources. In order to address the issue, this research has been carried out. To provide holistic consideration to the matter, comprehensive exploration of various causes of the water crisis and its impacts in developing countries were discussed. Then, various viable and relevant solutions to the problem have been thoroughly scrutinized, including scientific, rational, practical and speculative approaches, examination of existing methods, technologies and products at the BoP water market. The role of clean water to the sustainable development was specifically featured. The paper also has studied social and economic factors, actors and circumstances which affect the market development of clean water technologies in the BoP. Possibilities and potentials of successful business between foreign water enterprises and BoP consumers were considered, while primary obstacles are deliberated on, with suggestion of the ways to tackle them. Technologies and products which are needed by the poor must be affordable, sustainable and of an appropriate quality. The crucial question of technology transfer was soundly discussed with pointing out main hindrances on the way of its implementation between the developed and developing world. The means to overcome these barriers were properly observed as well. To explore to some extent the possibility and feasibility of technology transfer from Finland to the BoP sector, 3 case study analyses have been implemented. Personal discussions in form of interviews were conducted at Kemira, Outotec and Fenno Water, Finnish water treatment and supply enterprises. The results of the interviews shed light on the specific practical matters, actual obstacles and potential solutions of the technology transfer from Finland to low-income countries.