Deoxygenation of fatty acids for production of fuels and chemicals

The decreasing fossil fuel resources combined with an increasing world energy demand has raised an interest in renewable energy sources. The alternatives can be solar, wind and geothermal energies, but only biomass can be a substitute for the carbon–based feedstock, which is suitable for the production of transportation fuels and chemicals. However, a high oxygen content of the biomass creates challenges for the future chemical industry, forcing the development of new processes which allow a complete or selective oxygen removal without any significant carbon loss. Therefore, understanding and optimization of biomass deoxygenation processes are crucial for the future bio–based chemical industry. In this work, deoxygenation of fatty acids and their derivatives was studied over Pd/C and TiO2 supported noble metal catalysts (Pt, Pt–Re, Re and Ru) to obtain future fuel components. The 5 % Pd/C catalyst was investigated in semibatch and fixed bed reactors at 300 °C and 1.7–2 MPa of inert and hydrogen–containing atmospheres. Based on extensive kinetic studies, plausible reaction mechanisms and pathways were proposed. The influence of the unsaturation in the deoxygenation of model compounds and industrial feedstock – tall oil fatty acids – over a Pd/C catalyst was demonstrated. The optimization of the reaction conditions suppressed the formation of by–products, hence high yields and selectivities towards linear hydrocarbons and catalyst stability were achieved. Experiments in a fixed bed reactor filled with a 2 % Pd/C catalyst were performed with stearic acid as a model compound at different hydrogen–containing gas atmospheres to understand the catalyst stability under various conditions. Moreover, prolonged experiments were carried out with concentrated model compounds to reveal the catalyst deactivation. New materials were proposed for the selective deoxygenation process at lower temperatures (~200 °C) with a tunable selectivity to hydrodeoxygenation by using 4 % Pt/TiO2 or decarboxylation/decarbonylation over 4 % Ru/TiO2 catalysts. A new method for selective hydrogenation of fatty acids to fatty alcohols was demonstrated with a 4 % Re/TiO2 catalyst. A reaction pathway and mechanism for TiO2 supported metal catalysts was proposed and an optimization of the process conditions led to an increase in the formation of the desired products.

The re-introduction of oral entrance examinations at a translation studies department

Abstract

Re-usable ASIC integrationverification software architecture

Mikropiirien valmistus- ja suunnittelutekniikoiden kehittyminen mahdollistaa yhä monimutkaisempien mikropiirien valmistamisen. Piirien verifioinnista onkin tullut prosessin aikaa vievin osa,sillä kompleksisuuden kasvaessa kasvaa verifioinnin tarve eksponentiaalisesti. Vaikka erinäisiä strategioita piirien integroinnin verifiointiin on esitetty, mm. verifioinnin jakaminen koko suunnitteluprosessin ajalle, jopa yli puolet koko piirin suunnitteluun ja valmistukseen käytetystä työmäärästä kuluu verifiointiin. Uudelleenkäytettävät komponentit ovat pääosassa piirin suunnittelussa, mutta verifioinnissa uudelleenkäytettävyyttä ei ole otettu kunnolla käyttöön ainakaan verifiointiohjelmistojen osalta. Tämä diplomityö esittelee uudelleenkäytettävän mikropiirien verifiointiohjelmistoarkkitehtuurin, jolla saadaan verifiointitaakkaa vähennettyä poistamalla verifioinnissa käytettävien ohjelmistojen uudelleensuunnittelun ja toteuttamisen tarvetta.

Re-examination of Customer Satisfaction Measurement Results

Asiakastyytyväisyys on läheisesti yhteydessä yrityksen taloudelliseen menestykseen ja yrityksen yleisen laadun määrittämiseen. Asiakastyytyväisyyden mittaamista vaaditaan tällä hetkellä myös ISO 9001 laatujärjestelmästandardissa. Tämän vuoksi tarve tutkia ja mitata asiakastyytyväisyyttä on kasvanut yritysten ja yhteisöjen joukossa. Kokonaisvaltainen asiakastyytyväisyyden tutkiminen sisältää sekä asiakastyytyväisyyden mittaamista ja järjestelmällistä asiakaspalautteen tutkimista ja analysointia. Asiakastyytyväisyysmittaamisessa käytetään menettelytapoja ja tekniikoita, jotka ovat yleisesti käytössä markkinointitutkimuksessa. Menetelmiä on kuitenkin mukautettava, jotta ne sopivat asiakastyytyväisyyden mittaamiseksi. Asiakastyytyväisyysmittaustulosten perusanalyysit ovat helppo toteuttaa mutta tulokset voidaan helposti tulkita väärin ilman syvällisempiä tilastomatemaattisia analyysejä. Asiakastyytyväisyyden mittaaminen on helppo toteuttaa mutta tutkimussuunnitelma ja tulostenkeräysmenetelmä pitää suunnitella huolellisesti, jotta mittaustulosten luotettavuus ja validiteetti voidaan taata. Jotta asiakastyytyväisyyden tutkimisesta saataisiin maksimaalinen hyöty, pitäisi tutkimuksen myös tarkastella kuinka asiakastyytyväisyys, yrityksen sisäinen ja ulkoinen laatu sekä asiakaslojaalisuus ovat yhteydessä toisiinsa.

Minimization of the experimental workload for the prediction of pollutants propagation in rivers. Mathematical modelling and knowledge re-use

The present thesis in focused on the minimization of experimental efforts for the prediction of pollutant propagation in rivers by mathematical modelling and knowledge re-use. Mathematical modelling is based on the well known advection-dispersion equation, while the knowledge re-use approach employs the methods of case based reasoning, graphical analysis and text mining. The thesis contribution to the pollutant transport research field consists of: (1) analytical and numerical models for pollutant transport prediction; (2) two novel techniques which enable the use of variable parameters along rivers in analytical models; (3) models for the estimation of pollutant transport characteristic parameters (velocity, dispersion coefficient and nutrient transformation rates) as functions of water flow, channel characteristics and/or seasonality; (4) the graphical analysis method to be used for the identification of pollution sources along rivers; (5) a case based reasoning tool for the identification of crucial information related to the pollutant transport modelling; (6) and the application of a software tool for the reuse of information during pollutants transport modelling research. These support tools are applicable in the water quality research field and in practice as well, as they can be involved in multiple activities. The models are capable of predicting pollutant propagation along rivers in case of both ordinary pollution and accidents. They can also be applied for other similar rivers in modelling of pollutant transport in rivers with low availability of experimental data concerning concentration. This is because models for parameter estimation developed in the present thesis enable the calculation of transport characteristic parameters as functions of river hydraulic parameters and/or seasonality. The similarity between rivers is assessed using case based reasoning tools, and additional necessary information can be identified by using the software for the information reuse. Such systems represent support for users and open up possibilities for new modelling methods, monitoring facilities and for better river water quality management tools. They are useful also for the estimation of environmental impact of possible technological changes and can be applied in the pre-design stage or/and in the practical use of processes as well.

De re vestiaria

Invocatio: Q.F.F.Q.S.

Dissertatio metaphysica Kantianorum de re in se (Ding an sich) doctrinam breviter examinans. Quam cons. ampl. facult. philos. Aboënsis. Publico examini modeste offerunt Fredericus Bergbom

Painovuosi nimekkeestä.

Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Partie orientale de la Lapponie suèdoise. Tirée de celles d’Andr Burae(us) et de Isaac Massa. Par le Sr. Sanson geogr’ ord:re du roy

1 kartta : vär. ; 43,8 x 54,8 cm, lehti 46 x 56,7 cm.

Carelie, et l’Ingrie, ou Ingermenland. Par le S:r Sanson geogr’ ord:re du roy

La Carelie, et l’Ingrie, ou Ingermenland. Par le S:r Sanson geogr’ ord:re du roy. 1 kartta : vär. ; 46,7 x 55 cm, lehti 48,5 x 59,3 cm.

Cajanie, ou Bothnie orientale. Tirée de celles d’Andr Burae et de Isaac Massa. Par le S:r Sanson geogr’ ord:re du roy

1 kartta : vär. ; 43,7 x 58 cm, lehti 45,6 x 60 cm.

Superconducting properties and their enhancement in ReBa2Cu3O7-delta (RE = Y and Gd) films prepared by pulsed laser deposition

Due to font problem on the tilte field the titlte of the thesis is corrected here. The title of the thesis is: Superconducting properties and their enhancement in ReBa₂Cu₃O₇-delta (RE = Y and Gd) films prepared by pulsed laser deposition