Puun ja turpeen sekapolton vaikutus leijukerroskattilan hiukkaspäästöihin

Työn tavoitteena oli tutkia vaikuttaako puupolttoaineen lisääminen turpeen joukkoon leijukerroskattilan hiukkaspäästöihin tai sähkösuodattimen erotusasteeseen. Työn teoriaosassa selvitettiin hiukkaspäästöjen muodostumista leijukerrospoltossa ja vertailtiin eri polttotekniikoiden hiukkaspäästöjä. Lisäksi esiteltiin erilaisia hiukkasten erottamiseen soveltuvia erotuslaitteita. Tarkastelussa keskityttiin sähkösuodattimeen, joka on yleisin hiukkasten erottamiseen käytettävä erotuslaite. Työn kokeellinen osa suoritettiin turvetta ja puuta polttavalla kuplivalla leijukerroskattilalla. Kokeellisessa osassa tutkittiin vaikuttaako puun lisäys syntyvien hiukkasten kokojakaumiin, sähkösuodattimen jälkeiseen kokonaishiukkaspäästöön tai sähkösuodattimen erotusasteeseen. Kokeet suoritettiin sekä pelkkänä turpeenpolttona (2 koetta), että kahdella eri puu/turve-polttoainesuhteella. Kokojakaumamittaukset suoritettiin lisäksi kahdella eri menetelmällä. Kokojakaumamittausten perusteella todettiin puun lisäyksen kasvattavan pienhiukkasten muodostumista. Pienhiukkasten osuus kasvoi sekapolton myötä myös sähkösuodattimen jälkeen. Sekapoltolla ei sen sijaan ollut selvää vaikutusta kokonaishiukkaspäästöön tai sähkösuodattimen erotusasteeseen.

Jäännöshiilen ja kalkkikiven reaktiokinetiikan mallinnus kiertoleijukattilan tulipesässä

Työn tavoitteena oli kehittää mallit jäännöshiilen ja kalkkikiven reaktiokinetiikan sekä jäännöshiilen jauhautumisen ennustamiseksi kiertoleijukattilan tulipesässä. Kehitetyt mallit toimivat tulipesämallin osamalleina. Perustuen mallinnettuihin reaktionopeuksiin ja jauhautumiskäyttäytymiseen tulipesämalli ennustaa kalkkikivihiukkasten rikinsidonnan ja jäännöshiilen jakautumisen erikokoisiksi hiukkasiksi tulipesässä ja tuhkissa. Työssä kehitetyt mallit perustuvat olemassa oleviin kalkkikiven ja polttoaineen reaktiivisuustesteihin laboratorio-kokoluokan leijukerrosreaktorissa. Mallit huomioivat myös tulipesän olosuhteet. Menetelmät kelpoistettiin onnistuneesti kaupallisen kokoluokan kiertoleijukattiloista mitattujen ja tulipesämallilla laskettujen taseiden avulla. Mallien kehittämistä tullaan jatkamaan.

A system to assess the stability of airborne nanoparticle agglomerates under aerodynamic shear

Stability of airborne nanoparticle agglomerates is important for occupational exposure and risk assessment in determining particle size distribution of nanomaterials. In this study, we developed an integrated method to test the stability of aerosols created using different types of nanomaterials. An aerosolization method, that resembles an industrial fluidized bed process, was used to aerosolize dry nanopowders. We produced aerosols with stable particle number concentrations and size distributions, which was important for the characterization of the aerosols' properties. Next, in order to test their potential for deagglomeration, a critical orifice was used to apply a range of shear forces to them. The mean particle size of tested aerosols became smaller, whereas the total number of particles generated grew. The fraction of particles in the lower size range increased, and the fraction in the upper size range decreased. The reproducibility and repeatability of the results were good. Transmission electron microscopy imaging showed that most of the nanoparticles were still agglomerated after passing through the orifice. However, primary particle geometry was very different. These results are encouraging for the use of our system for routine tests of the deagglomeration potential of nanomaterials. Furthermore, the particle concentrations and small quantities of raw materials used suggested that our system might also be able to serve as an alternative method to test dustiness in existing processes.

Caracterização e estabilidade físico-química de sistemas poliméricos nanoparticulados para administração de fármacos

Polymeric nanoparticle systems such as nanocapsules and nanospheres present potential applications for the administration of therapeutic molecules. The physico-chemical characteristics of nanoparticle suspensions are important pre-requisites of the success of any dosage form development. The purpose of this review is to present the state of the art regarding the physico-chemical characterization of these drug carriers, in terms of the particle size distribution, the morphology, the polymer molecular weight, the surface charge, the drug content and the in vitro drug release profiles. Part of the review is devoted to the description of the techniques to improve the stability of colloidal systems.

Diagnostiikkamenetelmät höyrykattilan leijukerroksen tilan ja käytettävyysongelmien tunnistamiseksi

Diplomityön tavoitteena oli tutkia höyrykattiloiden leijukerrosten käytettävyysongelmia ja kirjallisuudesta löytyvien diagnostiikkamenetelmien toimivuutta leijukerroksen tilan ja käytettävyysongelmien tunnistamiseksi. Diagnostiikkamenetelmien toimivuutta testattiin VTT:n kiertoleijukoelaitteen prosessimittauksiin perustuen. Analysoinnissa käytettiin prosessimittauksia, jotka ovat yleisesti käytössä energiantuotannon leijukerroskattiloissa. Analysoitavina koeajotapauksina olivat kylmäkokeet partikkelikokojakaumaltaan vaihtelevalle leijutusmateriaalille, tuhkapartikkelien aiheuttama petimateriaalin karkeneminen ja agglomeroituminen, sekä vaihtelevien ajoarvojen vaikutus leijukerroksen hydrodynaamiseen käyttäytymiseen. Kokeellisesta osiosta saaduista tuloksista selvisi leijutusilman tilavuusvirran, petimassan ja partikkelikoon vaikutus analysoitavaan prosessimittaukseen. Tuloksista oli havaittavissa myös kiertävän petimateriaalin ja pohjapedin osuuksien vaikutus mitattuun painesignaaliin. Petipartikkelien agglomeroitumisen ja karkenemisen todettiin lisäävän kiertoleijukoelaitteistossa nousuputken pohjapedin määrää suhteessa kiertävään petimateriaaliin, mikä voitiin havaita painemittauksista.

Determinação direta de Ca, Mg, Mn e Zn em amostras de leite de búfala da Ilha de Marajó por espectrometria de absorção atômica com chama (FAAS)

This work proposes an analytical procedure for direct determination of calcium, magnesium, manganese and zinc in buffalo milk by flame atomic absorption spectrometry (FAAS). Samples were diluted with a solution containing 10% (v/v) of water-soluble tertiary amines (CFA-C) at pH 8. For comparison, buffalo milk samples were digested with HNO3 and H2O2. According to a paired t-test, the results obtained in the determination of Ca, Mg, Mn and Zn in digested samples and in 10% (v/v) CFA-C medium were in agreement at a 95% confidence level. The developed procedure is simple, rapid, decrease the possibility of contamination and can be applied for the routine determination of Ca, Mg, Mn and Zn in buffalo milk samples without any difficulty caused by matrix constituents, such as fat content, and particle size distribution in the milk emulsion.

Nanoemulsões óleo de laranja/água preparadas em homogeneizador de alta pressão

The objective of this work was to use the high-pressure homogenizer (HPH) to prepare stable oil/water nanoemulsions presenting narrow particle size distribution. The dispersions were prepared using nonionic surfactants based on ethoxylated ether. The size and distribution of the droplets formed, along with their stability, were determined in a Zetasizer Nano ZS particle size analyzer. The stability and the droplet size distribution in these systems do not present the significant differences with the increase of the processing pressure in the HPH). The processing time can promote the biggest dispersion in the size of particles, thus reducing its stability.

Production of silica gel from residual rice husk ash

This paper presents a study on the production of silica gel in hydrothermal process using residual rice husk ash. Measurements of the chemical composition, X-ray diffraction, infrared spectroscopy, particle size distribution, and pozzolanic activity were carried out in order to characterize the obtained material, and the optimal silica gel was selected for use as a mineral additive in cement pastes. The compressive strengths were determined for cement pastes containing silica gel (0.0, 2.5 or 5% by mass) in different times. The results indicate that the mixtures containing silica gel showed improved mechanical behavior over all time periods evaluated.

Síntese e caracterização de beads acrílicos preparados por polimerização em suspensão visando aplicação como excipiente farmacêutico para compressão direta

One of the difficulties reported for the suspension polymerization is control the size and granulometry of beads. The purpose of this work was to evaluate the use of cellulose nanowhiskers and mesoporous silica as stabilizers to reduce the size and the particle distribution. To monitor polymerization process was used FTIR-ATR spectroscopy. The morphology was analyzed by scanning electron microscopy. The particle size distribution was characterised using a CILAS granulometer. Thermal stability was studied by thermogravimetric analysis. The results indicated that cellulose nanowhiskers may provide stabilization and increase the thermal stability of the beads in contrast to mesoporous silica.

Synthesis, structural and morphological characterization of CeO2-ZnO nanosized powder systems from Pechini's method

This work reports on the investigation of nanosized CeO2-ZnO systems prepared by Pechini's method. The structural and morphological characterization of CeO2-ZnO systems as well as the characterization of CeO2 and ZnO separately, showed that the employed method result in powders with spheroidal particles whose size are in the range 30 - 200 nm, which is appropriate to provide homogeneous suspensions. The ZnO present in the prepared mixed oxides seems to increase particle size distribution and to influence the arrangement of the particles after powder dispersion.

Membrane emulsification in preparation of single site catalyst

In the theory part the membrane emulsification was studied. Emulsions are used in many industrial areas. Traditionally emulsions are prepared by using high shear in rotor-stator systems or in high pressure homogenizer systems. In membrane emulsification two immiscible liquids are mixed by pressuring one liquid through the membrane into the other liquid. With this technique energy could be saved, more homogeneous droplets could be formed and the amount of surfactant could be decreased. Ziegler-Natta and single-site catalysts are used in olefin polymerization processes. Nowadays, these catalysts are prepared according to traditional mixing emulsification. More homogeneous catalyst particles that have narrower particle size distribution might be prepared with membrane emulsification. The aim of the experimental part was to examine the possibility to prepare single site polypropylene catalyst using membrane emulsification technique. Different membrane materials and solidification techniques of the emulsion were examined. Also the toluene-PFC phase diagram was successfully measured during this thesis work. This phase diagram was used for process optimization. The polytetrafluoroethylene membranes had the largest contact angles with toluene and also the biggest difference between the contact angles measured with PFC and toluene. Despite of the contact angle measurement results no significant difference was noticed between particles prepared using PTFE membrane or metal sinter. The particle size distributions of catalyst prepared in these tests were quite wide. This would probably be fixed by using a membrane with a more homogeneous pore size distribution. It is also possible that the solidification rate has an effect on the particle sizes and particle morphology. When polymeric membranes are compared PTFE is probably still the best material for the process as it had the best chemical durability.

Characterization and use of swine deep bedding ashes in cementitious composites

The deep bedding is a swine alternative production, especially in the finishing phase, whose byproduct can be recycled, reducing the environmental impact. The objectives of this study were to characterize the ash coming from the controlled burning of the swine deep bedding (SDBA) based on rice husk, and to evaluate their performance in composites as a partial substitute for Portland cement (PC). To measure the differences between SDBA and rice husk ash (RHA) as a reference, we have characterized: particle size distribution, real specific density, x-ray diffraction, electrical conductivity, scanning electron microscopy, chemical analysis and loss on ignition. Samples were prepared for two experimental series: control, and another one with the partial replacement of 30% of SDBA in relation to the mass of the Portland cement. According to the results obtained for physical and mechanical characterization, the composites with SDBA can be used as a constructive element in the rural construction.

Morfologian hallinta nikkelin sulfidisaostuksessa

Diplomityön tarkoituksena oli tutkia nikkelin sulfidisaostuksessa syntyvien kiteiden morfologiaa ja siihen vaikuttavia parametreja. Syntyvien kiteiden kasvua ja morfologiaa tutkittiin kiteen muodostumisen ja kasvun teorioiden avulla. Saostuksen olosuhteet, kuten lämpötila, paine ja pH vaikuttavat muodostuvien kiteiden morfologiaan. Muilla parametreilla, kuten liuoksen ylikylläisyydellä, epäpuhtauksilla, lisäaineilla, sekoituksella ja reaktioajalla on myös suuri merkitys. Kokeiden avulla haluttiin liuoskoostumuksen, saostusolosuhteiden ja muiden komponenttien vaikutusta nikkelisulfidikiteiden morfologiaan. Kokeissa käytettiin kahta eri sulfidilähdettä: natriumvetysulfidia ja rikkivetyä. Puolipanoskokeissa nikkelipitoisuus oli 1,5 g/l, paine 101,3 kPa ja sekoitusnopeus 650 rpm. Saostuskokeet tehtiin natriumsulfaatti- 5 g/l ja ammoniumsulfaattiliuoksissa 300 g/l. Saostuskokeissa muuttujia olivat saostimen konsentraatio ja määrä, rauta- ja magne-siumepäpuhtaudet, lämpötila ja lisäaineet. Diplomityön kokeellisessa osassa morfologiaa tutkittiin suoraan valomikroskoopin ja pyyhkäisyelektronimikroskoopin (SEM) avulla. Morfologiaa tutkittiin myös epäsuorasti laskeutumisnopeuden, keskimääräisen partikkelikoon, ja ominaispinta-alamittausten avulla. Saostimen pitoisuuden vaikutukset partikkelimuotoon olivat pieniä, mutta vaikutukset ominaispinta-alaan ja partikkelikokoon olivat suuria. Natriumlauryylisul-faatti ja EDTA ohjasivat partikkelien rakennetta levymäisemmäksi, joka johti hitaaseen laskeutumisnopeuteen. Polyakryylihappo lisäaineena muuttaa partikkelien morfologiaa kuutiomaisemmaksi. Flokkulanttien ja raudan morfologiset vaikutukset olivat pieniä. Partikkelikoko ja omaispinta-ala pienenivät selvästi magnesiumpitoisuuden kasvaessa. Lämpötilan kasvattaminen lisäsi epäsäännöllisten kiteiden määrää ja muodostuneet kiteet olivat enemmän neulamaisia.

Helmimyllyn toimintaparametrien vaikutus jauhautuvuuteen

Työn teoriaosassa tutkittiin materiaalin hienontamista jauhatuksen näkökulmasta. Jauhatuksessa keskityttiin ultrahienojauhatukseen ja siinä käytettäviin myllyihin, jois-ta lähimmin tarkasteltiin helmimyllyä ja sen toimintaparametrien vaikutusta jauhau-tuvuuteen. Lisäksi teoriaosassa tutkittiin jauhatuksen energiankulutusta, joka on yksi jauhatuksen suurimmista ominaisuuksista. Työn kokeellisessa osassa tutkittiin kalkkikiven jauhautuvuutta ja jauhatuksen omi-naisenergiankulutusta käyttäen kolmea erilaista sekoitinelintä. Kokeissa myllynä käy-tettiin helmimyllyä ja jauhinkappaleina 2 mm:n lasihelmiä. Jauhautuvuutta tutkittiin analysoimalla tuotteiden partikkelikokojakaumat Beckman Coulter LS 13 320 partik-kelikokoanalysaattoria. Energiankulutukset määritettiin lietteen lämpötilan muutok-sen perusteella ensimmäisen viidentoista minuutin aikana. Työn tavoitteena oli selvittää, onko uusi lapamainen sekoitinelin tehokas jauhatta-vuuden kannalta mutta samalla myös energiatehokas. Tämän työn perusteella uusi lapamainen sekoitinelin on tehokas jauhautuvuuden kannalta suuremmilla pyörimis-nopeuksilla. Ominaisenergiankulutus on puolestaan samaa luokkaa suuremmilla pyö-rimisnopeuksilla verrattaessa eri sekoitinelimiä.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.