The Li+, Na+ and K+ ion exchange reaction process on the surface of mixed oxide SiO2/TiO2/Sb2O5 surface prepared by the sol-gel processing method

The porous mixed oxide SiO2/TiO2/Sb2O5 obtained by the sol-gel processing method presented a good ion exchange property and a high exchange capacity towards the Li+, Na+ and K+ ions. In the H+/M+ ion exchange process, the H+ / Na+ could be described as presenting an ideal character. The ion exchange equilibria of Li+ and K+ were quantitatively described with the help of the model of fixed tetradentate centers. The results of simulation evidence that for the H+ / Li+ exchange the usual situation takes place: the affinity of the material to the Li+ ions is decreased with increasing the degree of ion exchange. On the contrary, for K+ the effects of positive cooperativity, that facilitate the H+ / K+ exchange, were revealed.

Evaluation of the dioxin and furan formation thermodynamics in combustion processes of urban solid wastes

Specific combustion programs (Gaseq, Chemical equilibria in perfect gases, Chris Morley) are used to model dioxin and formation in the incineration processes of urban solid wastes. Thanks to these programs, it is possible to establish correlations with the formation mechanisms postulated in literature on the subject. It was found that minimum oxygen quantities are required to obtain a significant formation of these compounds and that more furans than dioxins are formed. Likewise, dioxin and furan formation is related to the presence of carbon monoxide, and dioxin and furan distribution among its different compounds depends on the chlorine and hydrogen relative composition. This is due to the fact that an increased chlorine availability leads to the formation of compounds bearing a higher chlorine concentration (penta-, hexa-, hepta-, and octachlorides), whereas an increased hydrogen availability leads to the formation of compounds bearing a lower chlorine number (mono, di-, tri-, and tetrachlorides).

Adsorption of hidrogen peroxide on the surface of silica - titania mixed oxide obtained by the sol-gel processing method

This work describes the sol-gel mixed oxide SiO2/TiO2 property, ST, as prepared, and submitted to heat treatment a 773 K, STC. SEM and EDS images show, within magnification used, a uniform distribution of the TiO2 particles in SiO2/TiO2 matrix. Both, ST and STC adsorb hydrogen peroxide on the surface and through EPR and UV-Vis diffuse reflectance spectra, it was possible to conclude that the species on the surface is the peroxide molecule attached to the Lewis acid site of titanium particle surface, alphaTi(H2O2)+. As the material is very porous, presumably the hydrogen peroxide molecule is confined in the matrix pores on the surface, a reason why the adsorbed species presents an exceptional long lived stability.

Ruokohelven käytön lisääminen Joensuun voimalaitoksen kattilassa – käytettävyys, hyötysuhde ja taloudellisuus

Ruokohelpi soveltuu ympäristöystävällisyyden ja korkean lämpöarvon vuoksi hyvin energiantuotantoon. Fortumin Joensuun voimalaitoksella ruokohelpi on syötetty kattilaan tähän asti pääasiassa pääpolttoaineisiin, turpeeseen tai hakkeeseen seostettuna pieninä energiaosuuksina. Pääpolttoaineisiin verrattuna ruokohelvellä on alhaisempi irto- ja energiatiheys, korkeampi klooripitoisuus ja kattilaa likaavampi tuhka, mikä asettaa rajoitteita sen käytön lisäämiselle voimalaitoksella. Alhaisesta irto- ja energiatiheydestä johtuvan holvautumisen sekä tukoksien lisääntymisen ja Joensuun voimalaitoksen nykyisten kuljettimien kapasiteettiongelmien vuoksi ruokohelven osuuden lisääminen suuremmaksi kuin 5 % polttoaine-energiasisällöstä on riskialtista ja edellyttää täten investointia erilliseen ruokohelven käsittely- ja syöttöjärjestelmään. Yksi vaihtoehto on murskata ruokohelpipaalit joko sähkökäyttöisellä, puolikiinteällä ja nopeakäyntisellä Haybuster H1130 tilt -murskaimella tai kiinteällä ja hidaskäyntisellä Raumaster-murskaimella ja ohjata ruokohelpisilppu joko pitkän mekaanisen kuljettimen ja sen perässä olevien lyhyiden pneumalinjojen tai pelkkien pitkien pneumalinjojen kautta suoraan kattilapesään. Työssä tutkitut investoinnit ovat taloudellisesti sitä kannattavampia mitä enemmän ruokohelpeä voidaan vuositasolla polttaa voimalaitoksella. Ruokohelven käyttömäärää voimalaitoksella kannattanee lisätä kuljetusmatkaa pidentämällä. Investointien valinta ei ole itsestäänselvyys. Nopeakäyntinen murskain on hidaskäyntistä murskainta edullisempi investointi, tosin hidaskäyntisen murskaimen käyttövarmuus on parempi kuin nopeakäyntisen murskaimen. Kattilan käytettävyyden kannalta ruokohelven käytön lisääminen edellyttää kattilan palamistekniikan analysointia laskennallisesti virtausmallinnuksella ennen kuin lopullisia päätöksiä investointien suhteen voidaan tehdä.

Model based study of a calcium oxide looping process for post-combustion carbon dioxide capture

Calcium oxide looping is a carbon dioxide sequestration technique that utilizes the partially reversible reaction between limestone and carbon dioxide in two interconnected fluidised beds, carbonator and calciner. Flue gases from a combustor are fed into the carbonator where calcium oxide reacts with carbon dioxide within the gases at a temperature of 650 ºC. Calcium oxide is transformed into calcium carbonate which is circulated into the regenerative calciner, where calcium carbonate is returned into calcium oxide and a stream of pure carbon dioxide at a higher temperature of 950 ºC. Calcium oxide looping has proved to have a low impact on the overall process efficiency and would be easily retrofitted into existing power plants. This master’s thesis is done in participation to an EU funded project CaOling as a part of the Lappeenranta University of Technology deliverable, reactor modelling and scale-up tools. Thesis concentrates in creating the first model frame and finding the physically relevant phenomena governing the process.

Lanthanum based high surface area perovskite-type oxide and application in CO and propane combustion

The perovskite-type oxides using transition metals present a promising potential as catalysts in total oxidation reaction. The present work investigates the effect of synthesis by oxidant co-precipitation on the catalytic activity of perovskite-type oxides LaBO3 (B= Co, Ni, Mn) in total oxidation of propane and CO. The perovskite-type oxides were characterized by means of X-ray diffraction, nitrogen adsorption (BET method), thermo gravimetric and differential thermal analysis (ATG-DTA) and X-ray photoelectron spectroscopy (XPS). Through a method involving the oxidant co-precipitation it's possible to obtain catalysts with different BET surface areas, of 33-44 m²/g, according the salts of metal used. The characterization results proved that catalysts have a perovskite phase as well as lanthanum oxide, except LaMnO3, that presents a cationic vacancies and generation for known oxygen excess. The results of catalytic test showed that all oxides have a specific catalytic activity for total oxidation of CO and propane even though the temperatures for total conversion change for each transition metal and substance to be oxidized.

Viscometric investigations and molecular interactions of some derivatives of 5-substituted indole dihydropyrimidines in mixed organic solvents

Colloid chemical behavior of indole dihydropyrimidines in non-aqueous solvent mixture benzene-methanol of varying composition has been investigated by viscometric measurements at 303K± 0.1. The viscosity of the system increases with the increase in concentration. The Trend Change Point (TCP) values have been determined by intersection of two straight lines, which are found to be dependent on the composition of solvent mixtures. The study confirms that the nature of synthesized compounds agglomerate formed below and above 50% benzene concentration is quite different. The viscometric data have been analyzed in terms of Einstein, Vand, Moulik and Jones-Dole equations. These well known equations have been successfully applied to explain the results of viscosity measurements and the viscometric parameters show that the behavior of compound changes in the proximity of 50% benzene concentration.

A study of combustion phenomena in circulating fluidized beds by developing and applying experimental and modelling methods for laboratory-scale reactors

The results shown in this thesis are based on selected publications of the 2000s decade. The work was carried out in several national and EC funded public research projects and in close cooperation with industrial partners. The main objective of the thesis was to study and quantify the most important phenomena of circulating fluidized bed combustors by developing and applying proper experimental and modelling methods using laboratory scale equipments. An understanding of the phenomena plays an essential role in the development of combustion and emission performance, and the availability and controls of CFB boilers. Experimental procedures to study fuel combustion behaviour under CFB conditions are presented in the thesis. Steady state and dynamic measurements under well controlled conditions were carried out to produce the data needed for the development of high efficiency, utility scale CFB technology. The importance of combustion control and furnace dynamics is emphasized when CFB boilers are scaled up with a once through steam cycle. Qualitative information on fuel combustion characteristics was obtained directly by comparing flue gas oxygen responses during the impulse change experiments with fuel feed. A one-dimensional, time dependent model was developed to analyse the measurement data Emission formation was studied combined with fuel combustion behaviour. Correlations were developed for NO, N2O, CO and char loading, as a function of temperature and oxygen concentration in the bed area. An online method to characterize char loading under CFB conditions was developed and validated with the pilot scale CFB tests. Finally, a new method to control air and fuel feeds in CFB combustion was introduced. The method is based on models and an analysis of the fluctuation of the flue gas oxygen concentration. The effect of high oxygen concentrations on fuel combustion behaviour was also studied to evaluate the potential of CFB boilers to apply oxygenfiring technology to CCS. In future studies, it will be necessary to go through the whole scale up chain from laboratory phenomena devices through pilot scale test rigs to large scale, commercial boilers in order to validate the applicability and scalability of the, results. This thesis shows the chain between the laboratory scale phenomena test rig (bench scale) and the CFB process test rig (pilot). CFB technology has been scaled up successfully from an industrial scale to a utility scale during the last decade. The work shown in the thesis, for its part, has supported the development by producing new detailed information on combustion under CFB conditions.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Ability of Aphis gossypii and Myzus persicae to Transmit Cucumber mosaic virus in Single and Mixed Infection with Two Potyviruses to Zucchini Squash

The main objective of this work was to investigate the ability of Aphis gossypii and Myzus persicae to transmit Cucumber mosaic virus (CMV) singly and mixed with two potyviruses (Papaya ringspot virus - type W, PRSV-W and Zucchini yellow mosaic virus, ZYMV), to zucchini squash plants (Cucurbita pepo). The results showed that the potyviruses in general were more efficiently transmitted by both species of aphids as compared to CMV. The transmission of PRSV-W, ZYMV and CMV separately was more efficient than in mixture.

Sähkön ja lämmön yhteistuotanto haasteellisilla polttoaineilla

Maailman energian kulutuksen lisääntymisen ja ilmastonmuutoksen myötä energiantuotannossa joudutaan jatkuvasti sopeutumaan muuttuviin tilanteisiin ja haasteisiin. Polttoteknillisiä haasteita aiheuttavat pelto- ja kierrätyspolttoaineet ovat lisäämässä osuuttaan uusiutuvien polttoaineiden joukossa. Jotta kyseisiä haasteellisia polttoaineita pystytään hyödyntämään, täytyy niiden aiheuttamat ongelmat tuntea ja laitevalmistajien kehittää niiden hyödyntämiseen sopivaa tekniikkaa. Tässä diplomityössä käydään läpi tulevaisuudessa käytettävät polttoaineet, nykyiset päästörajat, kiinteiden polttoaineiden poltto- ja kaasutustekniikat sekä likaantumis-, kuonaantumis- ja korroosiomekanismit voimalaitoskattiloissa. Työssä tutkitaan, onko haasteellisten polttoaineiden käyttöön investoiminen järkevää ja mikä nykypäivän tekniikoista on kannattavin. Myös välitulistuksen, lauhdeperän ja apujäähdyttimen kannattavuuksia vertaillaan sähkön ja lämmön yhteistuotannossa. Tuloksiksi saatiin, että edullisten peltobiomassojen ja kierrätyspolttoaineiden käyttäminen, joko perinteisten polttoaineiden seassa tai pääpolttoaineena, on nykyhinnoilla perinteisiin polttoaineisiin verrattuna kannattavaa. Investoiminen kierrätyspolttoaineiden valmistuslaitteisiin maksimoi kierrätyspolttoaineista saatavaa hyötyä. Välitulistuksen todettiin soveltuvan huonosti vastapaineprosessiin, sillä siitä saatava sähköntuotannon lisäys on hyvin pieni. Lauhdeperän ja apujäähdyttimen vertailuissa huomattiin, että lauhdeperä on kannattava investointi, jos sähkön ja lämmön hintaero pysyy tarpeeksi suurena. Haasteellisilla polttoaineilla pystytään pienentämään kasvihuonepäästöjä ja korvaamaan fossiilisten polttoaineiden käyttöä.

Evaluation of the throughfall and stemflow nutrient contents in mixed and pure plantations of Acacia mangium, Pseudosamenea guachapele and Eucalyptus grandis

The interception of the rainfall by the forest canopy has great relevance to the nutrient geochemistry cycle in low fertility tropical soils under native or cultivated forests. However, little is known about the modification of the rainfall water quality and hydrological balance after interception by the canopies of eucalyptus under pure and mixed plantations with leguminous species, in Brazil. Samples of rainfall (RF), throughfall (TF) and stemflow (SF) were collected and analyzed in pure plantations of mangium (nitrogen fixing tree -NFT), guachapele (NFT) and eucalyptus (non-nitrogen fixing tree -NNFT) and in a mixed stand of guachapele and eucalyptus in Seropédica, State of Rio de Janeiro, Brazil. Nine stemflow collectors (in selected trees) and nine pluviometers were randomly disposed under each stand and three pluviometers were used to measure the incident rainfall during 5.5 months. Mangium conveyed 33.4% of the total rainfall for its stem. An estimative based on corrections for the average annual precipitation (1213 mm) indicated that the rainfall's contribution to the nutrient input (kg ha-1) was about 8.42; 0.95; 19.04; 6.74; 4.72 and 8.71 kg ha-1 of N-NH4+, P, K+, Ca+2, Mg+2 and Na+, respectively. Throughfall provided the largest contributions compared to the stemflow nutrient input. The largest inputs of N-NH4+ (15.03 kg ha-1) and K+ (179.43 kg ha-1) were observed under the guachapele crown. Large amounts of Na+ denote a high influence of the sea. Mangium was the most adapted species to water competitiveness. Comparatively to pure stand of eucalyptus, the mixed plantation intensifies the N, Ca and Mg leaching by the canopy, while the inputs of K and P were lower under these plantations.

Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

GRANULOMETRIC INFLUENCE ON THE COMBUSTION OF CHARCOAL FOR BARBECUE1

The present work analyzed characteristics of charcoal used for barbecue and mainly took interest in the influence of the granulometry in the combustion process. The material have been tested for four different grain size (8, 16, 32 and 50 mm) following a combustion test called combustion index (ICOMcv), which takes in consideration time processing, temperature generated and the mass consumed. The characterization of charcoal was done according to the following parameters, moisture, apparent density, grain density, volatile materials content, ash content, fixed carbon content and calorific value. The proofed charcoal presented standard indicators for use in barbecue and was noticed the relationship between granulometric analysis and the ICOMcv. The 16 mm grain size charcoal sample showed the best results for combustion. By contrast, the largest grain size sample presented lower results compared to the other samples. Thus, establishing unprecedented quantitative indicators in relation to those observed in practice, regarding the influence of grain size on the efficiency of combustion of the charcoal when used for barbecue.