Calcination of aluminum hydroxide over pressure and residence time

This work investigates the possible effect of pressure and residence time to the reaction of aluminum hydroxide into aluminum oxide. Various pressurized conditions are used as well as the help of various residence times. The aim is to increase the conversion of the reaction with the use of different pressures and residence times. The tests were performed with a laboratory scale fluidized bed reactor at the Outotec R&D Center in Frankfurt. Additional test work such as particle size analysis and differential thermal analysis were also carried out. Some calcined samples were also characterized with X-ray diffraction at the University of Auckland to obtain a reaction pathway when using pressurized conditions. All of the results are then compared with previous results.

Rinnakkaispolttolaitoksen ympäristöntarkkailusuunnitelma

Diplomityössä päivitetään voimalaitoksen ympäristöntarkkailusuunnitelma vastaamaan uudistuneen ympäristöluvan ja lainsäädännön edellytyksiä. Työssä tutkitaan leijupetikatti-loiden tulipesän lämpötiloja, savukaasun viipymäaikoja tulipesässä, leijukerroskattiloiden päästöjä, päästöjen jatkuvatoimista mittaamista sekä päästöjen seurantaa ja raportointia. Tulipesän lämpötiloja mitattiin kupla- ja kiertoleijukattiloilla. Tuloksien perusteella havait-tiin kiertoleijukattilan tulipesän alaosan lämpötilojen olevan lähes riippumaton pedin lämpötilasta ja höyrykuormasta. Tulipesän yläosassa lämpötilat nousevat höyrykuorman kasvaessa, mutta pedin lämpötilalla ei havaittu vaikutusta tulipesän yläosassakaan. Molemmilla kattiloilla havaittiin voimakas vaakatasoinen lämpötilaprofiili. Kuplaleijukattilalla sekä höyrykuorma että pedin lämpötila vaikuttivat tulipesän lämpötilaan. Savukaasun teoreettiset viipymäajat laskettiin kiertoleijukattilalle. Laskelmien ja mittauksien perusteella havaittiin kattilalla mahdollisuus saavuttaa savukaasun kahden sekunnin viipymäaika 850 ºC lämpötilassa. Kattilan käyttäytymisen aukottomaksi selvittämiseksi kaikilla polttoaineseoksilla ja höyrykuormilla tarvitaan lisää toimenpiteitä kattilalla ja lisää tulipesän lämpötilamittauksia. Leijukerroskattiloiden päästöjen syntymistä ja hallintaa tutkittiin teoreettisesti kirjallisuustutkimuksena. Tutkittuihin päästöihin kuuluivat typen oksidit, rikkidioksidi, hiukkaset, hiilimonoksidi, orgaaninen kokonaishiili, suolahappo, fluorivety, raskasmetallit sekä dioksiinit ja furaanit. Jatkuvatoimisten päästömittausmittauslaitteiden toimintaperiaatteita selvitettiin kirjalli-suustutkimuksena. Samoin selvitettiin jatkuvatoimisten päästömittauslaitteiden virhelähtei-tä. Päästömittauslaitteille laadittiin pitkän ja lyhyen ajan laadunvarmistussuunnitelma. Ha-vaittiin, että nykyiset jatkuvatoimiset päästömittauslaitteet eivät täytä kaikkia uusia laatu-kriteereitä. Päästöjen jatkuvatoimiseen seuraamiseen työssä suunniteltiin uusi valvomonäyttö. Uuden näytön avulla tehostetaan päästöjen valvontaa. Päästöjen raportointiin työssä suunniteltiin vuorokausiraportti. Raporttiin kerätään jatkuva-toimisten päästömittauslaitteiden puolen tunnin keskiarvot. Raportin tarkastaa, allekirjoittaa ja arkistoi vuorossa oleva operaattori.

Synthesis of percarboxylic acids in microreactor

Percarboxylic acids are commonly used as disinfection and bleaching agents in textile, paper, and fine chemical industries. All of these applications are based on the oxidative potential of these compounds. In spite of high interest in these chemicals, they are unstable and explosive chemicals, which increase the risk of synthesis processes and transportation. Therefore, the safety criteria in the production process should be considered. Microreactors represent a technology that efficiently utilizes safety advantages resulting from small scale. Therefore, microreactor technology was used in the synthesis of peracetic acid and performic acid. These percarboxylic acids were produced at different temperatures, residence times and catalyst i.e. sulfuric acid concentrations. Both synthesis reactions seemed to be rather fast because with performic acid equilibrium was reached in 4 min at 313 K and with peracetic acid in 10 min at 343 K. In addition, the experimental results were used to study the kinetics of the formation of performic acid and peracetic acid. The advantages of the microreactors in this study were the efficient temperature control even in very exothermic reaction and good mixing due to the short diffusion distances. Therefore, reaction rates were determined with high accuracy. Three different models were considered in order to estimate the kinetic parameters such as reaction rate constants and activation energies. From these three models, the laminar flow model with radial velocity distribution gave most precise parameters. However, sulfuric acid creates many drawbacks in this synthesis process. Therefore, a ´´greener´´ way to use heterogeneous catalyst in the synthesis of performic acid in microreactor was studied. The cation exchange resin, Dowex 50 Wx8, presented very high activity and a long life time in this reaction. In the presence of this catalyst, the equilibrium was reached in 120 second at 313 K which indicates a rather fast reaction. In addition, the safety advantages of microreactors were investigated in this study. Four different conventional methods were used. Production of peracetic acid was used as a test case, and the safety of one conventional batch process was compared with an on-site continuous microprocess. It was found that the conventional methods for the analysis of process safety might not be reliable and adequate for radically novel technology, such as microreactors. This is understandable because the conventional methods are partly based on experience, which is very limited in connection with totally novel technology. Therefore, one checklist-based method was developed to study the safety of intensified and novel processes at the early stage of process development. The checklist was formulated using the concept of layers of protection for a chemical process. The traditional and three intensified processes of hydrogen peroxide synthesis were selected as test cases. With these real cases, it was shown that several positive and negative effects on safety can be detected in process intensification. The general claim that safety is always improved by process intensification was questioned.

Understanding the in vitro dissolution rate of glasses with respect to future clinical applications

Glass is a unique material with a long history. Several glass products are used daily in our everyday life, often unnoticed. Glass can be found not only in obvious applications such as tableware, windows, and light bulbs, but also in tennis rackets, windmill turbine blades, optical devices, and medical implants. The glasses used at present as implants are inorganic silica-based melt-derived compositions mainly for hard-tissue repair as bone graft substitute in dentistry and orthopedics. The degree of glass reactivity desired varies according to implantation situation and it is vital that the ion release from any glasses used in medical applications is controlled. Understanding the in vitro dissolution rate of glasses provides a first approximation of their behavior in vivo. Specific studies concerning dissolution properties of bioactive glasses have been relatively scarce and mostly concentrated to static condition studies. The motivation behind this work was to develop a simple and accurate method for quantifying the in vitro dissolution rate of highly different types of glass compositions with interest for future clinical applications. By combining information from various experimental conditions, a better knowledge of glass dissolution and the suitability of different glasses for different medical applications can be obtained. Thus, two traditional and one novel approach were utilized in this thesis to study glass dissolution. The chemical durability of silicate glasses was tested in water and TRIS-buffered solution at static and dynamic conditions. The traditional in vitro testing with a TRISbuffered solution under static conditions works well with bioactive or with readily dissolving glasses, and it is easy to follow the ion dissolution reactions. However, in the buffered solution no marked differences between the more durable glasses were observed. The hydrolytic resistance of the glasses was studied using the standard procedure ISO 719. The relative scale given by the standard failed to provide any relevant information when bioactive glasses were studied. However, the clear differences in the hydrolytic resistance values imply that the method could be used as a rapid test to get an overall idea of the biodegradability of glasses. The standard method combined with the ion concentration and pH measurements gives a better estimate of the hydrolytic resistance because of the high silicon amount released from a glass. A sensitive on-line analysis method utilizing inductively coupled plasma optical emission spectrometer and a flow-through micro-volume pH electrode was developed to study the initial dissolution of biocompatible glasses. This approach was found suitable for compositions within a large range of chemical durability. With this approach, the initial dissolution of all ions could be measured simultaneously and quantitatively, which gave a good overall idea of the initial dissolution rates for the individual ions and the dissolution mechanism. These types of results with glass dissolution were presented for the first time during the course of writing this thesis. Based on the initial dissolution patterns obtained with the novel approach using TRIS, the experimental glasses could be divided into four distinct categories. The initial dissolution patterns of glasses correlated well with the anticipated bioactivity. Moreover, the normalized surface-specific mass loss rates and the different in vivo models and the actual in vivo data correlated well. The results suggest that this type of approach can be used for prescreening the suitability of novel glass compositions for future clinical applications. Furthermore, the results shed light on the possible bioactivity of glasses. An additional goal in this thesis was to gain insight into the phase changes occurring during various heat treatments of glasses with three selected compositions. Engineering-type T-T-T curves for glasses 1-98 and 13-93 were stablished. The information gained is essential in manufacturing amorphous porous implants or for drawing of continuous fibers of the glasses. Although both glasses can be hot worked to amorphous products at carefully controlled conditions, 1-98 showed one magnitude greater nucleation and crystal growth rate than 13-93. Thus, 13-93 is better suited than 1-98 for working processes which require long residence times at high temperatures. It was also shown that amorphous and partially crystalline porous implants can be sintered from bioactive glass S53P4. Surface crystallization of S53P4, forming Na2O∙CaO∙2SiO2, was observed to start at 650°C. The secondary crystals of Na2Ca4(PO4)2SiO4, reported for the first time in this thesis, were detected at higher temperatures, from 850°C to 1000°C. The crystal phases formed affected the dissolution behavior of the implants in simulated body fluid. This study opens up new possibilities for using S53P4 to manufacture various structures, while tailoring their bioactivity by controlling the proportions of the different phases. The results obtained in this thesis give valuable additional information and tools to the state of the art for designing glasses with respect to future clinical applications. With the knowledge gained we can identify different dissolution patters and use this information to improve the tuning of glass compositions. In addition, the novel online analysis approach provides an excellent opportunity to further enhance our knowledge of glass behavior in simulated body conditions.

Modular continuous crystallizer: operation, experimental arrangement and identification of process parameters

Crystallization is employed in different industrial processes. The method and operation can differ depending on the nature of the substances involved. The aim of this study is to examine the effect of various operating conditions on the crystal properties in a chemical engineering design window with a focus on ultrasound assisted cooling crystallization. Batch to batch variations, minimal manufacturing steps and faster production times are factors which continuous crystallization seeks to resolve. Continuous processes scale-up is considered straightforward compared to batch processes owing to increase of processing time in the specific reactor. In cooling crystallization process, ultrasound can be used to control the crystal properties. Different model compounds were used to define the suitable process parameters for the modular crystallizer using equal operating conditions in each module. A final temperature of 20oC was employed in all experiments while the operating conditions differed. The studied process parameters and configuration of the crystallizer were manipulated to achieve a continuous operation without crystal clogging along the crystallization path. The results from the continuous experiment were compared with the batch crystallization results and analysed using the Malvern Morphologi G3 instrument to determine the crystal morphology and CSD. The modular crystallizer was operated successfully with three different residence times. At optimal process conditions, a longer residence time gives smaller crystals and narrower CSD. Based on the findings, at a constant initial solution concentration, the residence time had clear influence on crystal properties. The equal supersaturation criterion in each module offered better results compared to other cooling profiles. The combination of continuous crystallization and ultrasound has large potential to overcome clogging, obtain reproducible and narrow CSD, specific crystal morphologies and uniform particle sizes, and exclusion of milling stages in comparison to batch processes.

Ydinvoimalaitoksen vuosihuoltoajankohdan optimointi

Viimeaikoina ydinvoima on ollut vahvasti esillä mediassa. Keskustelut lisäydinvoimasta, sähköntuotantomuodoista, Olkiluodon kolmannen ydinvoimalaitosyksikön rakennustöistä, sähkön kulutuksen tulevaisuudesta ja nykyisestä taloustilanteesta ovat vaikuttaneet tarpeeseen tutkia sähkön tuotantokustannuksia ydinvoiman osalta. Tutkimuksessa keskitytään erityisesti ydinvoimalaitosyksiköiden vuosihuolto- ja polttoainekustannuksiin, jotka muodostavat suurimman suunnitellun yksittäisen kustannuserän ydinvoiman käyttöön liittyen. Työ tehdään Teollisuuden Voima Oyj:lle, joka pääsääntöisesti toimii Eurajoen Olkiluodossa. Työssä optimoidaan jokaiselle Olkiluodon ydinvoimalaitosyksikölle mahdollisimman edullinen vuosihuoltoajankohta. Optimaalisin ajankohta määrittyy edullisimman sähkön hinnan, ihanteellisimman käyttöjakson pituuden sekä resurssien saatavuuden perusteella. Ydinvoimalaitosyksiköiden vuosihuoltoajankohdat suunnitellaan siten, että vuosihuollot ovat kokonaisuudessaan ja laitosyksikkökohtaisesti optimaaliset. Työn lopputuloksena on esitys Olkiluodon ydinvoimalaitosyksiköiden optimaalisista vuosihuoltoajankohdista. Työn tuloksien myötä Teollisuuden Voima Oyj:llä on mahdollisuus pienentää vuosihuoltokustannuksiaan ja osaltaan vaikuttaa ydinvoimalla tuotetun sähkön kannattavuuteen. Vuosihuoltoajankohdan optimointi palvelee myös Teollisuuden Voima Oyj:n osakkaiden vaatimuksia.

Exit times for some processes with normally distributed noise

Denna avhandling handlar om metoder för att hitta begränsningar för det asymptotiska beteendet hos en förväntad uthoppstid från ett område omkring en xpunkt för processer som har normalfördelad störning. I huvudsak behandlas olika typer av autoregressiva processer. Fyra olika metoder används. En metod som använder principen för stora avvikelser samt en metod som jämför uthoppstiden med en återkomsttid ger övre begränsningar för den förväntade uthoppstiden. En martingalmetod och en metod för normalfördelade stokastiska variabler ger undre begränsningar. Metoderna har alla både förtjänster och nackdelar. Genom att kombinera de olika metoderna får man de bästa resultaten. Vi får fram gränsvärdet för det asymptotiska beteendet hos en uthoppstid för den multivariata autoregressiva processen, samt motsvarande gränsvärde för den univariata autoregressiva processen av ordning n.

The Cycle Times of Working Capital: Financial Value Chain Analysis Method

Interest towards working capital management increased among practitioners and researchers because the financial crisis of 2008 caused the deterioration of the general financial situation. The importance of managing working capital effectively increased dramatically during the financial crisis. On one hand, companies highlighted the importance of working capital management as part of short-term financial management to overcome funding difficulties. On the other hand, in academia, it has been highlighted the need to analyze working capital management from a wider perspective namely from the value chain perspective. Previously, academic articles mostly discussed working capital management from a company-centered perspective. The objective of this thesis was to put working capital management in a wider and more academic perspective and present case studies of the value chains of industries as instrumental in theoretical contributions and practical contributions as complementary to theoretical contributions and conclusions. The principal assumption of this thesis is that selffinancing of value chains can be established through effective working capital management. Thus, the thesis introduces the financial value chain analysis method which is employed in the empirical studies. The effectiveness of working capital management of the value chains is studied through the cycle time of working capital. The financial value chain analysis method employed in this study is designed for considering value chain level phenomena. This method provides a holistic picture of the value chain through financial figures. It extends the value chain analysis to the industry level. Working capital management is studied by the cash conversion cycle that measures the length (days) of time a company has funds tied up in working capital, starting from the payment of purchases to the supplier and ending when remittance of sales is received from the customers. The working capital management practices employed in the automotive, pulp and paper and information and communication technology industries have been studied in this research project. Additionally, the Finnish pharmaceutical industry is studied to obtain a deeper understanding of the working capital management of the value chain. The results indicate that the cycle time of working capital is constant in the value chain context over time. The cash conversion cycle of automotive, pulp and paper, and ICT industries are on average 70, 60 and 40 days, respectively. The difference is mainly a consequence of the different cycle time of inventories. The financial crisis of 2008 affected the working capital management of the industries similarly. Both the cycle time of accounts receivable and accounts payable increased between 2008 and 2009. The results suggest that the companies of the automotive, pulp and paper and ICT value chains were not able to self-finance. Results do not indicate the improvement of value chains position in regard to working capital management either. The findings suggest that companies operating in the Finnish pharmaceutical industry are interested in developing their own working capital management, but collaboration with the value chain partners is not considered interesting. Competition no longer occurs between individual companies, but between value chains. Therefore the financial value chain analysis method introduced in this thesis has the potential to support value chains in improving their competitiveness.

Cool Cats Don’t Dig the Squares” - The New York Times ja beat-sukupolvi, opiskelijamellakat ja hipit vuosina 1952-1969

Beat-sukupolvi, opiskelijoiden poliittinen aktiivisuus ja hipit olivat tunnettuja ilmiöitä Yhdysvalloissa 1950- ja 1960-luvuilla. Ilmiöillä oli paljon yhteistä ja ne vaikuttivat toisiinsa merkittävästi. Tätä yhteyttä ei aina tuoda esiin. Tämä tutkielma tuo esiin sen, miten The New York Times kirjoitti ilmiöistä. Tutkimus kertoo myös, miten The New York Times yhdistää ilmiöt keskenään. Sen lisäksi tulee esiin The New York Timesin näkemys ilmiöiden taustoista suhteessa nuorisokulttuuriin. Tutkimuksen kohteena on The New York Timesin lehtiartikkeleita vuosilta 1952-1969. Tutkimuksen pääkysymykset ovat: Miten The New York Times suhtautui beat-sukupolveen ja nuorisokulttuurin muutokseen? Miten The New York Times suhtautui yliopisto-opiskelijoihin ja heidän suhteeseensa nuorisokulttuurin muutokseen sekä miten The New York Times näkee hippien muuttavan yhteiskuntaa? Ensimmäistä pääkysymystä tarkastelen kahden alakysymyksen kautta: Miten beat-sukupolven synty esitetään The New York Timesissa, ja toisaalta millaisen kuvan The New York Times antaa beat-sukupolven vaikutuksesta nuorisoon? Toista pääkysymystä käsittelen kysymällä: Miten The New York Times näki nuorten poliittisen vaikuttavuuden nousun ja miten lehti suhtautui ajanjakson yliopistomellakoihin?. Kolmannessa luvussa tarkastelen pääkysymystä kysymällä: Keitä hipit olivat, ja olivatko hipit poliittisesti aktiivisia vai ei? Tutkimuksesta selviää, että The New York Times pyrkii kuvaamaan ilmiöitä mahdollisimman objektiivisesti. Lehti antaa ilmiöitä kuvatessa asioihin hyvin perehtyneiden henkilöiden esittää ilmiö. Sen jälkeen lehti antaa lukijoiden ja muiden asiantuntijoiden kommentoida. The New York Times näkee näiden ilmiöiden yhteyden ja se tulee voimakkaasti esille laajoissa artikkeleissa. Lyhyemmissä uutisissa yhteyttä ei aina näe, ja terminologia on yleistävämpi, tekstin eri tarkoitusperän takia. Kaiken kaikkiaan The New York Times tuo esiin mahdollisimman vähän moralisoivaa kuvaa ilmiöistä ja tuo esiin niiden keskinäisiä suhteita. Tuloksista näkee, että The New York Times on arvoiltaan vapaamielinen lehti, joka uutisoi, näiden aiheiden perusteella, kattavasti koko Yhdysvaltoja koskevista tapahtumista.

Open Access in Times of Knowledge Unlatched : Cooperative Action for Books and Journals

Presentation at the seminar "Publishers and Funders for OA in Finland", Helsinki, May 24, 2016