Uuttoprosessin suunnittelu

Teknologian kehitys ja prosessien tiukempi valvonta ovat alentaneet selluteollisuuden häviöitä tehden prosesseista suljetumpia. Valitettavasti nämä edistysaskeleet teknologiassa ovat lisänneet prosessiin kuulumattomien yhdisteiden määrää kemikaalien talteenottokierrossa. Näistä kemikaaleista haitallisimpia ovat kloridi- ja kaliumyhdisteet, jotka tulevat prosessiin raaka-aineiden ja prosessikemikaalien mukana. Kloridi ja kalium muodostavat emäksisissä liuoksissa epäorgaanisia liukoisia yhdisteitä, jotka rikastuvat lipeäkiertoon. Soodakattilassa kloridien läsnäolo alentaa tuhkan sulamislämpötilaa sekä tarttumispistettä, lisää korroosiota ja saostumien muodostumista kattilan pinnalle. Nämä seuraukset voivat vähentää vuosituotantoa ja nostaa korjauskustannuksia. Kaliumin ja kloridin rikastumista talteenottokiertoon voidaan estää poistamalla ne prosessista. Prosessiin kuulumattomat yhdisteet tulisi poistaa talteenottoprosessista ja säilyttää samalla korkea kemikaalien talteenottoprosentti. Koska kaliumin ja kloridin rikastumiskertoimet soodakattilan tuhkassa ovat korkeita, on tuhkan käsittely tehokasta. Kloridin ja kaliumin poistoon on kehitetty menetelmiä, joilla voidaan vähentää hyödyllisten kemikaalien häviöitä. Näitä menetelmiä ovat uutto, ioninvaihto, elektrodialyysi, jäähdytyskiteytys ja haihdutuskiteytys. Menetelmissä tuhka jaetaan kloridi- ja kaliumpitoiseen osaan ja natriumsulfaattipitoiseen osaan. Kloridi ja kalium poistetaan prosessista ja loput palautetaan lipeäkiertoon. Kloridin ja kaliumin poistoa tuhkasta tutkittiin uuttamalla tuhkaa vedellä. Parhaissa käyttöolosuhteissa natriumsulfaatin liukoisuus veteen on huomattavasti alhaisempi kuin kaliumkloridin liukoisuus veteen. Optimaalinen uuttolämpötila ja tuhka-vesisuhde määritettiin siten, että kloridi- ja kaliumpitoisuudet suodoksessa olivat mahdollisimman korkeat sekä natriumin ja muiden anioneiden pitoisuudet suodoksessa mahdollisimman alhaiset. Saatuja tuloksia käytettiin jatkuvatoimisen uuttoprosessin suunnittelussa.

Raakafosfaatin liuotus ja ammonointi

Apatiittien käyttöä raaka-aineena lannoitteiden valmistusprosessissa on usein hankaloittanut lannoitelietteen viskositeetin kasvu, kun hapanta lannoitelietettä on neutraloitu ammoniakilla. Työn tarkoituksena oli tutkia lannoitelietteen viskositeettiin vaikuttavia tekijöitä ja tekijöiden vaikutusta lannoitteen ominaisuuksiin. Työn kirjallisen osan alkupuoliskolla käsiteltiin raakafosfaatteja ja fosfaattilannoitteita. Tämän jälkeen keskityttiin lannoitteiden valmistukseen sekä viskositeetin merkitykseen lannoiteprosesseissa. Työn kokeellisessa osassa tutkittiin raakafosfaatin, liuotushapon, liuotushappomäärän, ammonointiajan sekä apatiitti/fosforihappo-suhteen vaikutusta lannoitteen ominaisuuksiin. Kokeet aloitettiin raakafosfaatin liuotuksella happoon. Tämän jälkeen liete neutraloitiin ammoniakilla ja suoritettiin muiden ravinteiden lisäys. Lannoitelietteen viskositeettiin voimakkaimmin vaikuttavat tekijät olivat kokeissa käytetty liuotushappo, ammonointiaika sekä raakafosfaatti. Raakafosfaatilla, liuotushapolla sekä apatiitti/fosforihappo-suhteella havaittiin olevan suurin merkitys lannoitteen fosforin vesiliukoisuudelle.

ELEKTRONIIKKATEHTAAN PAIKALLISESTIVALMISTETTUJEN KOMPONENTTIEN HANKINTAKETJUN KEHITTÄMINEN

Varastojen vähentämiseksi ehdotetaan usein eräkokojen pienentämistä. Tämä sopii sellaiseen toimintaympäristöön, jossa voidaan ostaa nimikkeitä oman valmistuksen ja myynnin tahdissa. Kun kiihkeärytmisessä elektroniikkabisneksessä alihankkijoilta ja varustetoimittajilta sitovasti tilataan hyvin lyhyellä toimitusajalla, ei oston eräkokojen pienentäminen kevennä materiaalivirtaa. Täytyy ottaa löysät pois hankintaketjun toimitusajoista. Monessa toimitusketjussa jalostava työ vaatii vain murto-osan toimitusajasta, ja loppuaika kuluu varastoissa odotteluun, kuljettamiseen ja moninkertaiseen tarkastamiseen. Hukka-ajan leikkaamisen ohessa haetaan muita kustannussäästöjä. Korkeiden työvoimakustannusten rasittama teollisuus on pyrkinyt teknisillä ratkaisuilla korvaamaan palkkatyövoiman erilaisilla mekaanisilla järjestelmillä. Pisimmällä ollaan pienerä- ja yksittäisvalmistusta harjoittavissa konepajoissa, joissa on investoitu FM-järjestelmiin. Diplomityössä on esitetty kaksi nivoutuvaa tutkimusprojektia, joista ensimmäinen keskittyy miehittämättömän käytön kehittämiseen ja toinen keventää hankintaketjun materiaalivirtaa. Ensin esiteltävä projekti on elektroniikkateollisuudelle uusi aluevaltaus. Siksi asiassa on jouduttu tekemään runsaasti perustutkimusta ja etenemään etappi kerrallaan. Projektin tuloksena on saatu aikaan automaattinen, joustava kuljetin, joka yksinään pystyy toimimaan ilman työvoimaa niin pitkään kunnes sen akut pitää ladata. Joustavan kuljettimen sisältävän järjestelmän muita elementtejä ei projektissa nostettu samalle miehittämättömän käytön tasolle, vaan ensin päätettiin hankkia kokemuksia kuljettimen toiminnasta. Toinen projekti syventää yhteistyötä yrityksen alihankkijan kanssa. Alihankkija on yksi harvojen Suomesta hankittavien komponenttien toimittaja. Siksi on pidetty tärkeänä tiivistää toimitusaikaa lähemmäs yrityksen sitovan tilauskannan pituutta. Tutkittavaksi valittiin mahdollisuus siirtää alihankkijan tuotantolaite yrityksen välittömään läheisyyteen, jolloin yrityksen tuotanto voisi tilata komponenttierän alihankkijan koneelta, kun se lähtötilanteessa tilataan komponenttivarastosta. Ennusteen perusteella tilattaisiin vain raaka-aine, mutta arvoa lisäävä työ tehtäisiin vain ja ainoastaan tilauksen mukaisesti.

Polttolaitosten päästöjen viranomaisraportoinnin uudistaminen

EU:n suurten polttolaitosten direktiivi (2001/80/EY) sekä jätteenpolttodirektiivi (2000/76/EY) aiheuttavat lähivuosina oleellisia muutoksia polttolaitosten päästöjen tarkkailuun. Nämä direktiivit on pantu täytäntöön Suomen lainsäädännössä vastaavina asetuksina. Tässä diplomityössä selvitettiin, mitä muutoksia uudistunut lainsäädäntö tuo polttolaitosten päästölaskentaan ja viranomaisraportointiin. Suurimpia muutoksia ovat päästöjen tarkkailujaksojen lyhentyminen, raja-arvojen tulkinnan muuttuminen, häiriö- sekä ylös- ja alasajojaksojen jättäminen pois pitoisuusraja-arvojen tarkkailusta sekä siirtyminen ominaispäästöjen (mg/MJ) laskennasta pitoisuusarvojen (mg/m3n) laskentaan. Päästötietojen raportoinnissa on huomioitava, että ympäristöhallinnon tavoitteena on siirtyä sähköisesti tapahtuvaan tiedonsiirtoon ja kuukausittain tapahtuvaan raportointiin kaikkien tarkkailtavien päästöjen osalta. Uudistunut ympäristölainsäädäntö koskee jo eräitä polttolaitoksia ja lopuillekin uudistuneet vaatimukset astuvat voimaan lähivuosien aikana. LCP-asetus koskee uusia laitoksia heti, olemassa oleville laitoksille uudet mittausvelvoitteet astuvat voimaan 27.11.2004 ja asetuksen mukaiset raja-arvot 1.1.2008 alkaen. Samoin jätteenpolttoasetus koskee uusia laitoksia heti, käytössä oleville laitoksille se astuu voimaan 29.12.2005. Ensimmäisen ympäristöluvan myöntämisajankohta määrää, luetaanko laitos uusiin vai olemassa tai käytössä oleviin laitoksiin. LCP-asetuksessa uusien ja olemassa olevien laitosten päästöjen tarkkailu poikkeaa hieman toisistaan. Jätteenpoltto- ja rinnakkaispolttolaitoksilla päästöjen tarkkailun toteutustapa puolestaan riippuu poltettavan jätteen laadusta ja sen määrän suhteesta muuhun polttoaineeseen. Lisäksi tämän diplomityöprojektin aikana laadittiin yksityiskohtaiset toteutusohjeet polttolaitoksia koskevan uudistuneen ympäristölainsäädännön mukaiselle päästöjen tarkkailulle ja raportoinnille. Ohjeet laadittiin erikseen LCP- ja jätteenpolttoasetusten soveltamiseksi sekä CO2-päästöjen määrittämistä varten. Ohjeita ei ole sisällytetty tähän työhön, vaan niitä kannattaa tiedustella Kontram Oy:ltä, mikäli niihin halutaan tutustua tarkemmin.

Soil quality assessment through a multi-approach analysis in soils of abandoned terraced land in NE Spain

The abandonment of agricultural land in mountainous areas has been an outstanding problem along the last century and has captured the attention of scientists, technicians and administrations, for the dramatic consequences sometimes occurred due to soil instability, steep slopes, rainfall regimes and wildfires. Hidromorfological and pedological alterations causing exceptional floods and accelerated erosion processes has therefore been studied, identifying the cause in the loss of landscape heterogeneity. Through the disappearance of agricultural works and drainage maintenance, slope stability has resulted severely affected. The mechanization of agriculture has caused the displacement of vines, olives and corks trees cultivation in terraced areas along the Mediterranean catchment towards more economically suitable areas. On the one hand, land use and management changes have implicated sociological changes as well, transforming areas inhabited by agricultural communities into deserted areas where the colonization of disorganized spontaneous vegetation has buried a valuable rural patrimony. On the other hand, lacking of planning and management of the abandoned areas has produced badlands and infertile soils due to wildfire and high erosion rates strongly degrading the whole ecosystems. In other cases, after land abandonment a process of soil regeneration has been recorded. Investigations have been conducted in a part of NE Spain where extended areas of terraced soils previously cultivated have been abandoned in the last century. The selected environments were semi-abandoned vineyards, semi-abandoned olive groves, abandoned stands of cork trees, abandoned stands of pine trees, scrubland of Cistaceaea, scrubland of Ericaceaea, and pasture. The research work was focused on the study of most relevant physical, chemical and biological soil properties, as well as runoff and erosion under soils with different plant cover to establish the abandonment effect on soil quality, due to the peculiarity and vulnerability of these soils with a much reduced depth. The period of observation was carried out from autumn 2009 to autumn 2010. The sediment concentration of soil erosion under vines was recorded as 34.52 g/l while under pasture it was 4.66 g/l. In addition, the soil under vines showed the least amount of organic matter, which was 12 times lower than all other soil environments. The carbon dioxide (CO2) and total glomalin (TG) ratio to soil organic carbon (SOC) in this soil was 0.11 and 0.31 respectively. However, the soil under pasture contained a higher amount of organic matter and showed that the CO2 and TG ratio to SOC was 0.02 and 0.11 respectively indicating that the soil under pasture better preserves the soil carbon pool. A similar trend was found in the intermediate soils in the sequence of land use change and abandonment. Soil structural stability increased in the two soil fractions investigated (0.25-2.00 mm, 2.0-5.6 mm) especially in those soils that did not undergo periodical perturbations like wildfires. Soil quality indexes were obtained by using relevant physical and chemical soil parameters. Factor analysis carried out to study the relationship between all soil parameters allowed to related variables and environments and identify those areas that better contribute to soil quality towards others that may need more attention to avoid further degradation processes

Photoluminescence of GaAs/AlGaAs quantum wells

In this thesis is studied the influence of uniaxial deformation of GaAs/AlGaAs quantum well structures to photoluminescence. Uniaxial deformation was applied along [110] and polarization ratio of photoluminescence at T = 77 K and 300 K was measured. Also the physical origin of photoluminescence lines in spectrum was determined and the energy band splitting value between states of heavy and light holes was estimated. It was found that the dependencies of polarization ratio on uniaxial deformation for bulk GaAs and GaAs/AlGaAs are different. Two observed lines in photoluminescence spectrum are induced by free electron recombination to energy sublevels of valence band corresponding to heavy and light holes. Those sublevels are splited due to the combination of size quantization and external pressure. The quantum splitting energy value was estimated. Also was shown a method, which allows to determine the energy splitting value of sublevels at room temperature and at comparatively low uniaxial deformation, when the other method for determining of the splitting becomes impossible.

Lexical Influences on Spoken Spondaic Word Recognition in Hearing-Impaired Patients.

Top-down contextual influences play a major part in speech understanding, especially in hearing-impaired patients with deteriorated auditory input. Those influences are most obvious in difficult listening situations, such as listening to sentences in noise but can also be observed at the word level under more favorable conditions, as in one of the most commonly used tasks in audiology, i.e., repeating isolated words in silence. This study aimed to explore the role of top-down contextual influences and their dependence on lexical factors and patient-specific factors using standard clinical linguistic material. Spondaic word perception was tested in 160 hearing-impaired patients aged 23-88 years with a four-frequency average pure-tone threshold ranging from 21 to 88 dB HL. Sixty spondaic words were randomly presented at a level adjusted to correspond to a speech perception score ranging between 40 and 70% of the performance intensity function obtained using monosyllabic words. Phoneme and whole-word recognition scores were used to calculate two context-influence indices (the j factor and the ratio of word scores to phonemic scores) and were correlated with linguistic factors, such as the phonological neighborhood density and several indices of word occurrence frequencies. Contextual influence was greater for spondaic words than in similar studies using monosyllabic words, with an overall j factor of 2.07 (SD = 0.5). For both indices, context use decreased with increasing hearing loss once the average hearing loss exceeded 55 dB HL. In right-handed patients, significantly greater context influence was observed for words presented in the right ears than for words presented in the left, especially in patients with many years of education. The correlations between raw word scores (and context influence indices) and word occurrence frequencies showed a significant age-dependent effect, with a stronger correlation between perception scores and word occurrence frequencies when the occurrence frequencies were based on the years corresponding to the patients' youth, showing a "historic" word frequency effect. This effect was still observed for patients with few years of formal education, but recent occurrence frequencies based on current word exposure had a stronger influence for those patients, especially for younger ones.

Image processing of false identity documents for forensic intelligence

Forensic intelligence has recently gathered increasing attention as a potential expansion of forensic science that may contribute in a wider policing and security context. Whilst the new avenue is certainly promising, relatively few attempts to incorporate models, methods and techniques into practical projects are reported. This work reports a practical application of a generalised and transversal framework for developing forensic intelligence processes referred to here as the Transversal model adapted from previous work. Visual features present in the images of four datasets of false identity documents were systematically profiled and compared using image processing for the detection of a series of modus operandi (M.O.) actions. The nature of these series and their relation to the notion of common source was evaluated with respect to alternative known information and inferences drawn regarding respective crime systems. 439 documents seized by police and border guard authorities across 10 jurisdictions in Switzerland with known and unknown source level links formed the datasets for this study. Training sets were developed based on both known source level data, and visually supported relationships. Performance was evaluated through the use of intra-variability and inter-variability scores drawn from over 48,000 comparisons. The optimised method exhibited significant sensitivity combined with strong specificity and demonstrates its ability to support forensic intelligence efforts.

Experimentos didáticos utilizando sistema de análise por injeção em fluxo

Didactic experiments are proposed in order to demonstrate the characteristics of flow injection analysis and to extend the applications of FIA to the determination of physical chemistry parameters in undergraduate labs. All experiments can be performed with the same flow manifold by employing usual FIA devices. Analytical characteristics are presented by means of the determination of iron in river water, employing 1,10-phenantroline as chromogenic reagent. Physical chemistry applications were the determination of reaction stoichiometries by continuous variation and mole-ratio methods and the evaluation of the pH and ionic strength effects on the kinetic of the reduction of hexacianoferrate(III) by ascorbic acid.

Pilarização de esmectita brasileira para fins catalíticos. Emprego de argila pilarizada na alquilação de benzeno com 1-dodeceno

Al-pillared clay was prepared with a Brazilian bentonite from the Campina Grande region (Paraíba, BRAZIL). It was intercalated at 298 K, during 48 hours, with a solution containing [Al3+] = 0.10 mol/L and molar ratio OH/Al = 2.0 prepared at 333 K, and was calcined at 773K. The catalytic activity was evaluated by alkylation of benzene with 1-dodecene. The characterization methods were: X-ray fluorescence and diffraction analysis; 27Al, 29Si and 23Na MAS NMR and textural analysis by N2 adsorption. The thermal stability of the natural clay was improved by the pillaring procedure, as well as the catalytic activity. The intercalated clay presented the highest initial rate of reaction among the systems tested.

Análise quiral por espectrometria de massas através da utilização do método cinético

Novel and quantitative mass spectrometry methods for rapid and accurate enantiomeric excess determination are presented. These methodologies use electrospray ionization (ESI) and mass spectrometry (MS) to detect and analyze, via collision-induced dissociation (CID), mass-selected transition metal complexes that promote enantio especific interactions. The data from CID are conveniently treated by the kinetic method, a sensitive linear free energy method of treating mass spectrometric results. Four different variations of this methodology are described: single ratio method (S R), quotient ratio method (Q R), fixed ligand method (S Rfixed), and quotient ratio method with fixed ligand (Q Rfixed). These individual methods are compared and their main features discussed in detail.

Alternativa potencial para aproveitamento do glicerol gerado na produção de biodiesel: síntese enzimática de monolaurina por esterificação

Esterification reactions of glycerol with lauric acid in solvent free system were carried out using lipases from several sources. All lipases were immobilized on polysiloxane-polyvinyl alcohol particles by covalent binding with high activity recovered. Among the tested enzymes, the Candida antarctica lipase allowed to attain the highest molar conversion (76%), giving similar proportions of monolaurin, dilaurin and low amount of trilaurin. To further improve the process, the Response Surface Methodology (RSM) was used and optima temperature and molar ratio glycerol to lauric acid were found to be 45 ºC and 5:1, respectively. Under these conditions, 31.35% of monolaurin concentrations were attained and this result was in close agreement with the statistical model prediction.

UTILIZAÇÃO DO COMPÓSITO NANOESTRUTURADO SIO2/TIO2NA FOTODEGRADAÇÃO DE CORANTES TÊXTEIS COM LUZ SOLAR NATURAL

SiO2/TiO2 nanostructured composites with three different ratios of Si:Ti were prepared using the sol-gel method. These materials were characterized using energy dispersive X-ray fluorescence, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, photoluminescence, Raman with Fourier transform infrared spectroscopy, and the specific surface area. The band gaps of materials were determined by diffuse reflectance spectra, and the values of 3.20 ± 0.01, 2.92 ± 0.02, and 2.85 ± 0.01 eV were obtained as a result of the proportional increases in the amount of Ti within the composite. The materials exhibit only the anatase (TiO2) crystalline phase and have crystalline domains ranging from 4 to 5 nm. The photodegradation process of methylene blue, royal blue GRL, and golden yellow GL dyes were studied with respect to their contact times, pH variations within the solution, and the variations in the dye concentration of the solution in response to only sunlight. The maximum amount of time for the mineralization of dyes was 90 min. The kinetics of the process follows an apparently first order model, in which the obtained rate constant values were 5.72 × 10-2 min-1 for methylene blue, 6.44 × 10-2min-1 for royal blue GRL, and 1.07 × 10-1min-1 for golden yellow.

Identification of Races of Selected Isolates of Uromyces appendiculatus from Minas Gerais (Brazil) Based on the new international classification system

Twelve single-pustule isolates of Uromyces appendiculatus, the etiological agent of common bean rust, were collected in the state of Minas Gerais, Brazil, and classified according to the new international differential series and the binary nomenclature system proposed during the 3rd Bean Rust Workshop. These isolates have been used to select rust-resistant genotypes in a bean breeding program conducted by our group. The twelve isolates were classified into seven different physiological races: 21-3, 29-3, 53-3, 53-19, 61-3, 63-3 and 63-19. Races 61-3 and 63-3 were the most frequent in the area. They were represented by five and two isolates, respectively. The other races were represented by just one isolate. This is the first time the new international classification procedure has been used for U. appendiculatus physiological races in Brazil. The general adoption of this system will facilitate information exchange, allowing the cooperative use of the results obtained by different research groups throughout the world. The differential cultivars Mexico 309, Mexico 235 and PI 181996 showed resistance to all of the isolates that were characterized. It is suggested that these cultivars should be preferentially used as sources for resistance to rust in breeding programs targeting development lines adapted to the state of Minas Gerais.

Permanent Magnet Synchronous Machine for Parallel Hybrid Vehicle

The aim of this thesis is to describe hybrid drive design problems, the advantages and difficulties related to the drive. A review of possible hybrid constructions, benefits of parallel, series and series-parallel hybrids is done. In the thesis analytical and finite element calculations of permanent magnet synchronous machines with embedded magnets were done. The finite element calculations were done using Cedrat’s Flux 2D software. This machine is planned to be used as a motor-generator in a low power parallel hybrid vehicle. The boundary conditions for the design were found from Lucas-TVS Ltd., India. Design Requirements, briefly: • The system DC voltage level is 120 V, which implies Uphase = 49 V (RMS) in a three phase system. • The power output of 10 kW at base speed 1500 rpm (Torque of 65 Nm) is desired. • The maximum outer diameter should not be more than 250 mm, and the maximum core length should not exceed 40 mm. The main difficulties which the author met were the dimensional restrictions. After having designed and analyzed several possible constructions they were compared and the final design selected. Dimensioned and detailed design is performed. Effects of different parameters, such as the number of poles, number of turns and magnetic geometry are discussed. The best modification offers considerable reduction of volume.