Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

Rasvaisten jätevesien puhdistus

Rasvaisten jätevesien puhdistus on sitä tuottaville yrityksille kallista ja hankalaa. Nykyisten päästövaatimusten saavuttaminen on perinteisillä jätevedenkäsittelymenetelmillä vaikeaa tai lähes mahdotonta, riippuen käsiteltävän jäteveden ominaisuuksista. Rasvaisen jäteveden käsittelyssä on käytetty mm. laskeutusta, flotaatiota, hydrosykloneja, pisaroitusta, suodatusta sekä biologista käsittelyä. Lisäksi happohydrolyysiä voidaan soveltaa edellä mainittujen menetelmien esikäsittelynä. Useita näitä erotusmenetelmiä voidaan myös tehostaa kemikaalien lisäyksellä. Työn kirjallisuusosassa on käsitelty rasvaisten jätevesien ja emulsioiden kalvosuodatusta ja kalvojen käyttöä pisaroituselementtinä. Tavanomaisessa kalvosuodatuksessa tarkoituksena on erottaa kalvoa läpäisemätön rasvajae ja permeoituva vesijae toisistaan, kun taas pisaroittamisen tarkoituksena on saada dispergoituneen faasin pisarakoko kasvamaan joko kalvon pinnalla tai sen huokosissa. Pisarakoon kasvaessa emulsion stabiilisuus heikkenee ja faasit voidaan helpommin erottaa toisistaan. Työn kokeellisessa osassa tavoitteena oli tutkia kalvosuodatuksen ja erilaisten kalvojen toimivuutta esteröintilaitoksen rasvaisten jätevesien käsittelyssä. Tutkimuksessa käytettiin MW- (GE Osmonics), C30F- (Nadir Filtration), Teflon Typar- (Tetratex) sekä JX-kalvoa (Osmonics Desal). Haastetta työhön syntyi tutkittujen jätevesien ominaisuuksien suuresta vaihtelusta sitä tuottavan laitoksen panostyylisestä toiminnasta johtuen. Lisäksi tutkittiin, onko syöttöliuoksen pH-säädöllä ja laskeutuksella ennen suodatusta merkittävää etua itse kalvosuodatusprosessiin. Kalvotekniikkaa voidaan tämän tutkimuksen perusteella soveltaa myös esteröintilaitoksen rasvaisten jätevesien suodatukseen, ja erityistä etua saadaan jäteveden pH-säädöllä (pH 3) ja laskeutuksella ennen varsinaista suodatusta. Tällaiseen käsittelyyn soveltuu tutkituista kalvoista parhaiten hydrofiilinen regeneroidusta selluloosasta valmistettu C30F-kalvo, jonka etuna on vähäinen foulaantuminen muihin tutkittuihin kalvoihin verrattuna.

The health promotion model and rare disease patients : a mixed methods study examining adherence to treatment in men with congenital hypogonadotropic hypogonadism

Rare diseases are typically chronic medical conditions of genetic etiology characterized by low prevalence and high complexity. Patients living with rare diseases face numerous physical, psychosocial and economic challenges that place them in the realm of health disparities. Congenital hypogonadotropic hypogonadism (CHH) is a rare endocrine disorder characterized by absent puberty and infertility. Little is known about the psychosocial impact of CHH on patients or their adherence to available treatments. This project aimed to examine the relationship between illness perceptions, depressive symptoms and adherence to treatment in men with CHH using the nursing-sensitive Health Promotion Model (HPM). A community based participatory research (CBPR) framework was employed as a model for empowering patients and overcoming health inequities. The study design used a sequential, explanatory mixed-methods approach. To reach dispersed CHH men, we used web-based recruitment and data collection (online survey). Subsequently, three patient focus groups were conducted to provide explanatory insights into the online survey (i.e. barriers to adherence, challenges of CHH, and coping/support) The online survey (n=101) revealed that CHH men struggle with adherence and often have long gaps in care (40% >1 year). They experience negative psychosocial consequences because of CHH and exhibit significantly increased rates of depression (p<0.001). Focus group participants (n=26) identified healthcare system, interpersonal, and personal factors as barriers to adherence. Further, CHH impacts quality of life and impedes psychosexual development in these men. The CHH men are active internet users who rely on the web forcrowdsourcing solutions and peer-to-peer support. Moreover, they are receptive to web-based interventions to address unmet health needs. This thesis contributes to nursing knowledge in several ways. First, it demonstrates the utility of the HPM as a valuable theoretical construct for understanding medication adherence and for assessing rare disease patients. Second, these data identify a range of unmet health needs that are targets for patient-centered interventions. Third, leveraging technology (high-tech) effectively extended the reach of nursing care while the CBPR approach and focus groups (high-touch) served as concurrent nursing interventions facilitating patient empowerment in overcoming health disparities. Last, these findings hold promise for developing e-health interventions to bridge identified shortfalls in care and activating patients for enhanced self- care and wellness -- Les maladies rares sont généralement de maladies chroniques d'étiologie génétique caractérisées par une faible prévalence et une haute complexité de traitement. Les patients atteints de maladies rares sont confrontés à de nombreux défis physiques, psychosociaux et économiques qui les placent dans une posture de disparité et d'inégalités en santé. L'hypogonadisme hypogonadotrope congénital (CHH) est un trouble endocrinien rare caractérisé par l'absence de puberté et l'infertilité. On sait peu de choses sur l'impact psychosocial du CHH sur les patients ou leur adhésion aux traitements disponibles. Ce projet vise à examiner la relation entre la perception de la maladie, les symptômes dépressifs et l'observance du traitement chez les hommes souffrant de CHH. Cette étude est modélisée à l'aide du modèle de la Promotion de la santé de Pender (HPM). Le cadre de l'approche communautaire de recherche participative (CBPR) a aussi été utilisé. La conception de l'étude a reposé sur une approche mixte séquentielle. Pour atteindre les hommes souffrant de CHH, un recrutement et une collecte de données ont été organisées électroniquement. Par la suite, trois groupes de discussion ont été menées avec des patients experts impliqués au sein d'organisations reliés aux maladies rares. Ils ont été invités à discuter certains éléments additionnels dont, les obstacles à l'adhésion au traitement, les défis généraux de vivre avec un CHH, et l'adaptation à la maladie en tenant compte du soutien disponible. Le sondage en ligne (n = 101) a révélé que les hommes souffrant de CHH ont souvent de longues périodes en rupture de soins (40% > 1 an). Ils vivent des conséquences psychosociales négatives en raison du CHH et présentent une augmentation significative des taux de dépression (p <0,001). Les participants aux groupes de discussion (n = 26) identifient dans l'ordre, les systèmes de soins de santé, les relations interpersonnelles, et des facteurs personnels comme des obstacles à l'adhésion. En outre, selon les participants, le CHH impacte négativement sur leur qualité de vie générale et entrave leur développement psychosexuel. Les hommes souffrant de CHH se considèrent être des utilisateurs actifs d'internet et comptent sur le web pour trouver des solutions pour trouver des ressources et y recherchent le soutien de leurs pairs (peer-to-peer support). En outre, ils se disent réceptifs à des interventions qui sont basées sur le web pour répondre aux besoins de santé non satisfaits. Cette thèse contribue à la connaissance des soins infirmiers de plusieurs façons. Tout d'abord, elle démontre l'utilité de la HPM comme une construction théorique utile pour comprendre l'adhésion aux traitements et pour l'évaluation des éléments de promotion de santé qui concernent les patients atteints de maladies rares. Deuxièmement, ces données identifient une gamme de besoins de santé non satisfaits qui sont des cibles pour des interventions infirmières centrées sur le patient. Troisièmement, méthodologiquement parlant, cette étude démontre que les méthodes mixtes sont appropriées aux études en soins infirmiers car elles allient les nouvelles technologies qui peuvent effectivement étendre la portée des soins infirmiers (« high-tech »), et l'approche CBPR par des groupes de discussion (« high-touch ») qui ont facilité la compréhension des difficultés que doivent surmonter les hommes souffrant de CHH pour diminuer les disparités en santé et augmenter leur responsabilisation dans la gestion de la maladie rare. Enfin, ces résultats sont prometteurs pour développer des interventions e-santé susceptibles de combler les lacunes dans les soins et l'autonomisation de patients pour une meilleure emprise sur les auto-soins et le bien-être.

Sisäisten donorien vaikutus Polypropeeni Ziegler-Natta katalyytissä

Tässä työssä tutkittiin erilaisten sisäisten donorien vaikutusta polypropeenin ominaisuuksiin käytettäessä Ziegler-Natta-katalyyttiä, joka valmistettiin Borealiksen aiemmin kehittämällä kaksifaasimenetelmällä. Tällä uudella menetelmällä katalyytti voidaan valmistaa ilman lisättyä sisäistä donoria ja kantajaa. Katalyyttihiukkaset saadaan kaksifaasisysteemin ansiosta muodoltaan pyöreiksi. Työn kokeellisessa osassa valmistettiin erilaisia Mg-komplekseja, jossa sisäinen donori muodostuu in-situ alkoholin ja karboksyylihappokloridin reagoidessa keskenään. Katalyyttisynteesissä Mg-kompleksi reagoi TiCl4:n kanssa. Saatujen katalyyttien ominaisuuksia testattiin polymeroimalla niillä propeenia 70 °C:ssa tunnin ajan. Polymeerien ominaisuuksia tutkittiin useiden eri karakterisointimenetelmien avulla. Lisäksi tutkittiin mahdollisuutta valmistaa katalyytti, joka ei sisältäisi ftalaattia. Työssä havaittiin, että katalyytin valmistusmenetelmä on käyttökelpoinen myös muilla sisäisillä donoreilla kuin referenssinä käytetyllä DOP:lla. Kaksiliuosfaasi-systeemi saatiin aikaan myös kahdella muulla työssä tutkitulla sisäisellä donorilla. Lisäksi faasitasapainokokeissa kahden liuosfaasin systeemi saatiin aikaan sisäisellä donorilla, joka ei sisältänyt ftalaattia. Kyseisellä katalyytillä havaittiin olevan muista katalyyteistä poikkeavia ominaisuuksia. Esimerkiksi se antoi matalamman isotaktisuuden kuin referenssikatalyytti ja se saattaisikin soveltua matalan isotaktisuuden pehmeille tuotteille. Työssä kokeiltiin yhdellä uudella katalyytillä myös eteenin polymerointia, sillä katalyytin donoripitoisuus oli hyvin matala. Katalyytin aktiivisuus eteenipolymeroinnissa oli varsin hyvä.

What is the potential of spread in invasive bryophytes?

Although the number of invasive bryophytes is much lower than that of higher plants, they threaten habitats that are often species rich and of high conservation relevance. Their potential of spread has, however, never been determined. Here, we assess whether the three most invasive bryophyte species shifted their niche during the invasion process and whether the extent of the study area defined to calibrate the model (geographic background, GB) affects model transferability. We then determine whether ecological niche models (ENMs) developed in their native range can be projected in other areas to assess their invasive potential. The macroclimatic niches of Campylopus introflexus, Orthodontium lineare and Lophocolea semiteres were compared in their native range (Southern Hemisphere) and in their invasion range (Northern Hemisphere) using ordination techniques. ENMs from an ensemble model were calibrated in the native range and projected onto the Northern Hemisphere using different GBs. No evidence for niche expansion in the invaded range was found and the species occur in the invaded range under climate conditions that are similar to those in the native range. The performance of the models to predict occurrences in the invaded range increased with the extent of the GB. The potential range of all species included entire regions on continents where they are still absent. The expansion of the investigated species appears to be constrained by climate conditions that are similar to those currently prevailing in their native range, which is consistent with our failure to demonstrate macroclimatic niche shift in the invaded range. The use of large GBs is recommended in such vagile organisms with large, disjunct distributions. The models indicated that invasive bryophyte species might become a threat in central and eastern Europe, North America and eastern Asia if accidentally introduced or naturally dispersed.

Congenital tracheal anomalies.

Congenital tracheal lesions are rare, but important, causes of morbidity in infants and children. Consequently, experience in their management is limited and dispersed. Given its small diameter, the juvenile trachea is obstructed easily by various natural causes, or following a surgical intervention. The diagnosis of a congenital, tracheal, obstructive anomaly is based on a high degree of suspicion in infants and children with respiratory distress accompanied by retraction. In this article, the authors discuss the various causes of these conditions, their diagnostic features, and the treatment possibilities.

Kaasutuskaasun puhdistus

Tässä diplomityössä on selvitetty hiilestä, jätteestä tai biopolttoaineesta kaasutetun kaasun märkä- ja kuivapuhdistusta. Kaasutuskaasun puhdistuksella voidaan likainen ja jopa ongelmallinen aines muuttaa tai puhdistaa sellaiseksi ympäristökelpoiseksi polttoaineeksi, että sitä voidaan käyttää nykyisissä kulutuskohteissa ongelmitta. Lisäkannustusta kaasutuskaasun puhdistus saa uusista EU-direktiiveistä, jotka tulevat rajoittamaan jätteiden läjittämistä kaatopaikoille. Loppusijoitukseen meneviä jätevirtoja voidaan energiakäytöllä pienentää huomattavasti.Työ on tehty PVO-Engineering Oy:n voimalaitostekniikan osastolle kevään 2001 aikana. Työn tavoitteena oli kasvattaa yrityksen tietomäärää kaasutuskaasun puhdistuksen osalta. Lisäksi pyrittiin selvittämään uuden keraamisen pussisuodatinmateriaalin käyttöä kaasutuskaasun kuumakuivasuodatuksessa. Työn ensimmäisessä osassa esitetään kaasutuskaasun koostumuksen ja syntymisen lisäksi tämän työn lähtökohdat ja tavoitteet. Toisessa osassa selvitetään kaasulle asetettavia vaatimuksia eri käyttötapojen mukaan. Kolmannessa ja neljännessä osassa selvitetään puhdistettavien komponenttien käyttäytymistä ja sopivia puhdistusmenetelmiä.Kaasutuskaasun puhdistustekniikka vaihtelee paljonkin riippuen kaasun käyttökohteesta. Eroja syntyy käyttökohteen asetettamista vaatimuksista polttoaineelle, kaasutettavan polttoaineen koostumuksesta ja laadun vaihtelusta. Puhdistuksessa keskitytään kloori -, rikki -, typpi - ja metalliyhdisteiden poistamiseen kaasuvirrasta. Erotuskyvyllä arvioituna eri puhdistusmenetelmistä tehokkaimpia ovat pesurisähkösuodatinyhdistelmät. Niiden suuret jätemäärät ovat kuitenkin iso ongelma. Kuumakuivapuhdistuksessa pyritään kehittämään menetelmä, jossa syntyvät jätemäärät ovat pieniä ja puhdistustulos on riittävä. Puhdistuksen apukeinona käytetään usein erilaisia katalyyttejä. Tunnetuimpia ovat erilaiset kalsiumpohjaiset materiaalit ja mineraalit. Katalyyteillä voidaan tehostaa tarpeellisia kemiallisia reaktioita puhdistusprosessissa. Kaikki puhdistukseen liittyvät ongelmat ovat kooltaan niin suuria, että niiden ratkaisemiseksi on tulevaisuudessa tehtävä lujasti töitä. Markkinanäkymät toimivalle puhdistustekniikalle ovat nykymaailmassa hyvät. Niinpä tuotekehitykseen laitetut panokset voivat tulevaisuudessa olla yritykselle kullan arvoisia.

Venäjän ruoan vähittäiskauppasektorin rakenne ja kehitys suomalaisen elintarviketeollisuuden näkökulmasta

This research paper focuses on the Russian food retail sector and its structure and development. At the moment it is one of the fastest growing markets today. The growth originates from high oil price, which has been accumulated to people’s wages. But even though the income increases, the share of food of all retail trade has been fairly stable. Thus, the consumption is shifting to products with more quality and value. The share of modern retail outlets is low, as the Russian retail sector is still very dispersed to traditional retail outlets such as kiosks, open markets and small grocery stores. The store chains are, however, becoming more and more significant. The biggest market for retailers is Moscow but nowadays the chains are expanding rapidly into the other regions. Even though the markets have not been saturated in Moscow, the best prospects for growth are in the regions. The most important factor restricting the growth in Moscow is the availability of real estate and land plots for stores. The market is moving forward to saturation, and a consolidation process will follow. This process has already started but not many acquisitions have been made so far. To this point the domestic chains have settled to form alliances. The chains are trying to enhance their power in price negotiations by forming purchasing alliances, introducing private label goods and using the regional expansion as a striking weapon. In order to follow the growing chains to other regions the producer must sell its products to the chains at favorable terms. Suppliers are strong in negotiations when they have a functioning distribution network, ability to JIT-deliveries, proper documentation policies, a strong brand, reliability in deliveries and a fair price. The size of the entry ticket, i.e. the listing fee may define the shelf space a producer gets in the stores.

Kationinvaihtohartsien hapetuskestävyys

Hyvin puhdasta vettä vaativissa sovelluksissa käytettävät kationinvaihtohartsit eivät saisi vuotaa puhdistettavaan veteen mitään vieraita aineita. Todellisuudessa hartsit kuitenkin vuotavat hyvin pieniä määriä erilaisia yhdisteitä käytön aikana. Aineet, joita kationinvaihtohartsi päästää veteen, ovat osaksi hartsin polymerointireaktion aikana sen rungon sisään jääneitä yhdisteitä. Nämä voidaan suurimmaksi osaksi poistaa pesemällä hartsia. Osittain niitä syntyy myös hartsin polystyreenidivinyylibentseenirungon (PS-DVB) hapettuessa. Hapettumisen seurauksena syntyneet yhdisteet ovat pääosin orgaanisia sulfonaatteja. Tämä työ koskee ydinvoimalaitoksissa käytettäviä pulverihartseja, joita käytetään primääripiirissä kiertävän lauhdeveden puhdistukseen ja jotka joutuvat siellä alttiiksi hapettumiselle. Yleensä hapettuminen on hidasta ja se johtuu veteen liuenneesta hapesta. Hapettuminen nopeutuu huomattavasti, jos vedessä on läsnä hapettimia tai siirtymämetalli-ioneja. Tällaisia hapettimia ovat esimerkiksi vetyperoksidi, otsoni, vapaa kloori, typpihappo ja kromi. Vetyperoksidin vaikutuksesta hartsin runkoon muodostuu hydroperoksidiryhmä, jonka hajoamisesta alkaa reaktioiden sarja, joka lopulta johtaa hartsin polymeerirungon katkeamiseen. Siirtymämetalli-ionit katalysoivat peroksidien hajoamista. Tavallisimpia hapetusta katalysoivia metalli-ioneja ovat rauta ja kupari, joiden katalyyttinen aktiivisuus on suuri. Tässä työssä pyrittiin selvittämään, onko mahdollista valmistaa hartseja, jotka kestävät hapettumista paremmin kuin nykyisin käytössä olevat hartsit. Sen tutkimiseksi tehtiin kiihdytettyjä hapetuskokeita käyttäen hapettimena vetyperoksidia ilman siirtymämetalli-ioni katalyyttejä. Hapetuskokeet tehtiin kaupallisesti saatavilla hartseilla ja uusilla työtä varten syntetisoiduilla koehartseilla. Hapetuskokeiden etenemistä seurattiin mittaamalla veteen liuenneiden orgaanisten aineiden kokonaismäärää (TOC-analyysi) ja liuoksessa esiintyvien orgaanisten sulfonaattien määrää johtokykymittauksin. Saadut tulokset antoivat viitteitä siitä, että hartsin synteesiolosuhteilla voi olla suurempi vaikutus sen hapetuskestävyyteen kuin synteesissä käytetyillä raaka-aineilla.

Removal of Lipophilic Wood Extractives from TMP Process Waters by Wet Oxidation

Työssä tutkittiin kokeellisesti rasvaliukoisten uuteaineiden poistamista TMP -prosessin vesikierroista märkähapetuksen avulla. Työn tavoitteena oli tutkia mahdollisuudet hyödyntää TMP -prosessissa vallitsevaa korkeaa lämpötilaa rasvaliukoisten uuteaineiden poistamiseen hapettamalla niitä puhtaalla hapella. Kirjallisuusosassa tarkasteltiin märkähapetuksen teknologiaa, reaktiomekanismia, käytettyjä katalyyttejä, käyttökohteita sekä kustannuksia. Kokeita suoritettiin autoklaavireaktorissa lämpötiloissa 140 °C, 160 °C ja 180 °C. Vetyperoksidia käytettiin katalyyttinä lisätyn vetyperoksidin määrän ollessa 100 - 1800 mg/l ja hapen osapaineen ollessa 0 ( typpiatmosfääri) - 15 baria. Kokeissa tarkasteltiin kemiallisen hapenkulutuksen (COD), rasvaliukoisten uuteaineiden konsentraation, orgaanisen kokonaishiilen (TOC) ja värin muutoksia kokeiden aikana eri lämpötiloilla, hapen osapaineilla ja lisätyn vetyperoksidin määrillä. Kokeissa saavutettiin 30 %:n COD:n vähenemä sekä 90 %:n vähenemä rasvaliukoisissa uuteaineissa lämpötiloissa 160 °C ja 180 °C. Lisäämällä vetyperoksidia katalyyttinä saavutettiin lähes sama tulos lämpötilassa 140 °C. Suurin tässä työssä havaittu ongelma oli lisääntynyt värinmuodostus vedessä olevassa hienojakoisessa kiintoaineessa hapetuksen aikana. Tämän vuoksi lisätutkimukset ovat tarpeellisia sen seikan selvittämiseksi, voidaanko muodostunut väri mahdollisesti poistaa massan valkaisussa.

Lipase Improvement: Goals and strategies

Lipases have received great attention as industrial biocatalysts in areas like oils and fats processing, detergents, baking, cheese making, surface cleaning, or fine chemistry . They can catalyse reactions of insoluble substrates at the lipid-water interface, preserving their catalytic activity in organic solvents. This makes of lipases powerful tools for catalysing not only hydrolysis, but also various reverse reactions such as esterification, transesterification, aminolysis, or thiotransesterifications in anhydrous organic solvents. Moreover, lipases catalyse reactions with high specificity, regio and enantioselectivity, becoming the most used enzymes in synthetic organic chemistry. Therefore, they display important advantages over classical catalysts, as they can catalyse reactions with reduced side products, lowered waste treatment costs, and under mild temperature and pressure conditions. Accordingly, the use of lipases holds a great promise for green and economical process chemistry.

Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane"s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

Particle shape and orientation in laser diffraction and static image analysis size distribution analysis of micrometer sized rectangular particles

Laser diffraction (LD) and static image analysis (SIA) of rectangular particles [United States Pharmacopeia, USP30-NF25, General Chapter <776>, Optical Miroscopy.] have been systematically studied. To rule out sample dispersion and particle orientation as the root cause of differences in size distribution profiles, we immobilize powder samples on a glass plate by means of a dry disperser. For a defined region of the glass plate, we measure the diffraction pattern as induced by the dispersed particles, and the 2D dimensions of the individual particles using LD and optical microscopy, respectively. We demonstrate a correlation between LD and SIA, with the scattering intensity of the individual particles as the dominant factor. In theory, the scattering intensity is related to the square of the projected area of both spherical and rectangular particles. In traditional LD the size distribution profile is dominated by the maximum projected area of the particles (A). The diffraction diameters of a rectangular particle with length L and breadth B as measured by the LD instrument approximately correspond to spheres of diameter ØL and ØB respectively. Differences in the scattering intensity between spherical and rectangular particles suggest that the contribution made to the overall LD volume probability distribution by each rectangular particle is proportional to A2/L and A2/B. Accordingly, for rectangular particles the scattering intensity weighted diffraction diameter (SIWDD) explains an overestimation of their shortest dimension and an underestimation of their longest dimension. This study analyzes various samples of particles whose length ranges from approximately 10 to 1000 μm. The correlation we demonstrate between LD and SIA can be used to improve validation of LD methods based on SIA data for a variety of pharmaceutical powders all with a different rectangular particle size and shape.

Aluminium fouling and its impact on activated carbon based dioxin and furan removal in a wet scrubber at a co-incineration plant

Dioxins and furans, PCDD/Fs, are highly toxic substances formed in post combustion zones in furnaces. PCDD/F emissions are regulated by a waste incineration directive which relates also to co-incineration plants. Several observations of dioxin and furan enhancements in wet scrub- bers have been reported previously. This is thought to be due to the so-called "memory effect" which occurs when dioxins and furans absorb into plastic material in scrubbers and desorb when ambient circumstances alter significantly. At the co-incineration plant involved, dioxins and furans are controlled with a wet scrubber, the tower packing of which is made of plastic in which activated carbon particles are dispersed. This should avoid the memory effect and act as a dioxin and furan sink since dioxins and furans are absorbed irreversibly into the packing ma- terial. In this case, the tower packing in the scrubber is covered with a white layer that has been found to be mainly aluminium. The aim of this thesis was to determine the aluminium balance and the dioxin and furan behaviour in the scrubber and, thus, the impacts that the foul- ing has on dioxin and furan removal. The source of aluminium, reasons for fouling and further actions to minimize its impacts on dioxin and furan removal were also to be discovered. Measurements in various media around the scrubber and in fuels were made and a profile analysis of PCDD/F and mass balance calculations were carried out. PCDD/F content de- creased in the scrubber. The reduced PCDD/F was not discharged into scrubbing water. The removal mechanism seems to work in spite of the fouling, at least with low PCDD/F loads. Most of the PCDD/F in excess water originates from the Kymijoki River which is used as feeding water in the scrubber. Fouling turned out to consist mainly of aluminium hydroxides. Sludge combusted in the furnace was found to be a significant source of aluminium. Ways to minimize the fouling would be adjustment of pH to a proper lever, installation of a mechanical filter to catch the loose material from the scrubbing water and affecting the aluminium content of the sludge.

Imaging techniques applied for detection of secretion, transgene delivery and G proteincoupled receptors in reproductive and endocrine cells in vivo and in vitro

Post-testicular sperm maturation occurs in the epididymis. The ion concentration and proteins secreted into the epididymal lumen, together with testicular factors, are believed to be responsible for the maturation of spermatozoa. Disruption of the maturation of spermatozoa in the epididymis provides a promising strategy for generating a male contraceptive. However, little is known about the proteins involved. For drug development, it is also essential to have tools to study the function of these proteins in vitro. One approach for screening novel targets is to study the secretory products of the epididymis or the G protein-coupled receptors (GPCRs) that are involved in the maturation process of the spermatozoa. The modified Ca2+ imaging technique to monitor release from PC12 pheochromocytoma cells can also be applied to monitor secretory products involved in the maturational processes of spermatozoa. PC12 pheochromocytoma cells were chosen for evaluation of this technique as they release catecholamines from their cell body, thus behaving like endocrine secretory cells. The results of the study demonstrate that depolarisation of nerve growth factor -differentiated PC12 cells releases factors which activate nearby randomly distributed HEL erythroleukemia cells. Thus, during the release process, the ligands reach concentrations high enough to activate receptors even in cells some distance from the release site. This suggests that communication between randomly dispersed cells is possible even if the actual quantities of transmitter released are extremely small. The development of a novel method to analyse GPCR-dependent Ca2+ signalling in living slices of mouse caput epididymis is an additional tool for screening for drug targets. By this technique it was possible to analyse functional GPCRs in the epithelial cells of the ductus epididymis. The results revealed that, both P2X- and P2Y-type purinergic receptors are responsible for the rapid and transient Ca2+ signal detected in the epithelial cells of caput epididymides. Immunohistochemical and reverse transcriptase-polymerase chain reaction (RTPCR) analyses showed the expression of at least P2X1, P2X2, P2X4 and P2X7, and P2Y1 and P2Y2 receptors in the epididymis. Searching for epididymis-specific promoters for transgene delivery into the epididymis is of key importance for the development of specific models for drug development. We used EGFP as the reporter gene to identify proper promoters to deliver transgenes into the epithelial cells of the mouse epididymis in vivo. Our results revealed that the 5.0 kb murine Glutathione peroxidase 5 (GPX5) promoter can be used to target transgene expression into the epididymis while the 3.8 kb Cysteine-rich secretory protein-1 (CRISP-1) promoter can be used to target transgene expression into the testis. Although the visualisation of EGFP in living cells in culture usually poses few problems, the detection of EGFP in tissue sections can be more difficult because soluble EGFP molecules can be lost if the cell membrane is damaged by freezing, sectioning, or permeabilisation. Furthermore, the fluorescence of EGFP is dependent on its conformation. Therefore, fixation protocols that immobilise EGFP may also destroy its usefulness as a fluorescent reporter. We therefore developed a novel tissue preparation and preservation techniques for EGFP. In addition, fluorescence spectrophotometry with epididymal epithelial cells in suspension revealed the expression of functional purinergic, adrenergic, cholinergic and bradykinin receptors in these cell lines (mE-Cap27 and mE-Cap28). In conclusion, we developed new tools for studying the role of the epididymis in sperm maturation. We developed a new technique to analyse GPCR dependent Ca2+ signalling in living slices of mouse caput epididymis. In addition, we improved the method of detecting reporter gene expression. Furthermore, we characterised two epididymis-specific gene promoters, analysed the expression of GPCRs in epididymal epithelial cells and developed a novel technique for measurement of secretion from cells.