Radiaalikompressorin aerodynaaminen suunnittelu

Tämän diplomityön tavoitteena on ollut suunnitella radiaalikompressori. Aluksi on tutustuttu radiaalikompressorissa tapahtuviin ilmiöihin, jonka jälkeen radiaalikompressori on suunniteltu. Reunaehtoina suunnittelussa olivat toimilaitteelta saatava teho 250 kW ja sen suurin pyörimisnopeus 500 Hz. Esisuunnittelu on tehty Virtaustekniikan laboratoriossa kehitetyllä CentriFlow-ohjelmalla. Juoksupyörän muoto on suunniteltu viskoosittomilla 2D-malleilla. Juoksupyörän muodon suunniittelussa on käytetty kaupallista AxCent-ohjelmaa. Juoksupyörän muoto on tarkistettu laskennallisen virtausdynamiikan avulla. Virtausmallinnuksessa käytettiin FinFlo-ohjelmaa. Suunnittelun ja mallinnuksen pohjalta valittiin kolme erilaista juoksupyörää valmistukseen.

Pressure filtration characteristics of enzymatically hydrolyzed biomass suspensions

Enzymatic hydrolysis of lignocellulosic polymers is likely to become one of the key technologies enabling industrial production of liquid biofuels and chemicals from lignocellulosic biomass. Certain types of enzymes are able to hydrolyze cellulose and hemicellulose polymers to shorter units and finally to sugar monomers. These monomeric sugars are environmentally acceptable carbon sources for the production of liquid biofuels, such as bioethanol, and other chemicals, such as organic acids. Liquid biofuels in particular have been shown to contribute to the reduction of net emissions of greenhouse gases. The solid residue of enzymatic hydrolysis is composed mainly of lignin and partially degraded fibers, while the liquid phase contains the produced sugars. It is usually necessary to separate these two phases at some point after the hydrolysis stage. Pressure filtration is an efficient technique for this separation. Solid-liquid separation of biomass suspensions is difficult, because biomass solids are able to retain high amounts of water, which cannot be readily liberated by mechanical separation techniques. Most importantly, the filter cakes formed from biomaterials are compressible, which ultimately means that the separation may not be much improved by increasing the filtration pressure. The use of filter aids can therefore facilitate the filtration significantly. On the other hand, the upstream process conditions have a major influence on the filtration process. This thesis investigates how enzymatic hydrolysis and related process conditions affect the filtration properties of a cardboard suspension. The experimental work consists of pressure filtration and characterization of hydrolysates. The study provides novel information about both issues, as the relationship between enzymatic hydrolysis conditions and subsequent filtration properties has so far not been considered in academic studies. The results of the work reveal that the final degree of hydrolysis is an important factor in the filtration stage. High hydrolysis yield generally increases the average specific cake resistance. Mixing during the hydrolysis stage resulted in undefined changes in the physical properties of the solid residue, causing a high filtration resistance when the mixing intensity was high. Theoretical processing of the mixing data led to an interesting observation: the average specific cake resistance was observed to be linearly proportional to the mixer shear stress. Another finding worth attention is that the size distributions of the solids did not change very dramatically during enzymatic hydrolysis. There was an observable size reduction during the first couple of hours, but after that the size reduction was minimal. Similarly, the size distribution of the suspended solids remained almost constant when the hydrolyzed suspension was subjected to intensive mixing. It was also found that the average specific cake resistance was successfully reduced by the use of filter aids. This reduction depended on the method of how the filter aids were applied. In order to obtain high filtration capacity, it is recommended to use the body feed mode, i.e. to mix the filter aid with the slurry prior to filtration. Regarding the quality of the filtrate, precoat filtration was observed to produce a clear filtrate with negligible suspended solids content, while the body feed filtrates were turbid, irrespective of which type of filter aid was used.

Novel technology for preparation of optically active chemicals

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

The usage of experimental research in business-to-business marketing context in academic marketing journals

The aim of this master’s thesis is to introduce what is experimental research and how the researcher is able to use this researching method in business-to-business context. This work has been done with analyzing articles of four academic marketing journals from years 1992-2012. In the literature part there is introduction of the nature of the experimental research, its terminology and design. There is also discussion about limitations of experimental research and comparison of experimental research to quasi-experimental design. In the results part there is a review how experimental research has been used in the business-to-business context in the past two decades. In the analysis there is introduction of themes, samplings, different kinds of variables and main findings. The work offers a good understanding to nature of experimental research and useful data for organizing a real experimental study.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

Analysis and modelling of chemical looping combustion process with and without oxygen uncoupling

Effective control and limiting of carbon dioxide (CO₂) emissions in energy production are major challenges of science today. Current research activities include the development of new low-cost carbon capture technologies, and among the proposed concepts, chemical combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) have attracted significant attention allowing intrinsic separation of pure CO₂ from a hydrocarbon fuel combustion process with a comparatively small energy penalty. Both CLC and CLOU utilize the well-established fluidized bed technology, but several technical challenges need to be overcome in order to commercialize the processes. Therefore, development of proper modelling and simulation tools is essential for the design, optimization, and scale-up of chemical looping-based combustion systems. The main objective of this work was to analyze the technological feasibility of CLC and CLOU processes at different scales using a computational modelling approach. A onedimensional fluidized bed model frame was constructed and applied for simulations of CLC and CLOU systems consisting of interconnected fluidized bed reactors. The model is based on the conservation of mass and energy, and semi-empirical correlations are used to describe the hydrodynamics, chemical reactions, and transfer of heat in the reactors. Another objective was to evaluate the viability of chemical looping-based energy production, and a flow sheet model representing a CLC-integrated steam power plant was developed. The 1D model frame was succesfully validated based on the operation of a 150 kWth laboratory-sized CLC unit fed by methane. By following certain scale-up criteria, a conceptual design for a CLC reactor system at a pre-commercial scale of 100 MWth was created, after which the validated model was used to predict the performance of the system. As a result, further understanding of the parameters affecting the operation of a large-scale CLC process was acquired, which will be useful for the practical design work in the future. The integration of the reactor system and steam turbine cycle for power production was studied resulting in a suggested plant layout including a CLC boiler system, a simple heat recovery setup, and an integrated steam cycle with a three pressure level steam turbine. Possible operational regions of a CLOU reactor system fed by bituminous coal were determined via mass, energy, and exergy balance analysis. Finally, the 1D fluidized bed model was modified suitable for CLOU, and the performance of a hypothetical 500 MWth CLOU fuel reactor was evaluated by extensive case simulations.

Forecasting financial weather - can we foresee market sentiment? Quantitative analysis of nodal prices in the New Zealand Electricity Spot Market

Time series of hourly electricity spot prices have peculiar properties. Electricity is by its nature difficult to store and has to be available on demand. There are many reasons for wanting to understand correlations in price movements, e.g. risk management purposes. The entire analysis carried out in this thesis has been applied to the New Zealand nodal electricity prices: offer prices (from 29 May 2002 to 31 March 2009) and final prices (from 1 January 1999 to 31 March 2009). In this paper, such natural factors as location of the node and generation type in the node that effects the correlation between nodal prices have been reviewed. It was noticed that the geographical factor affects the correlation between nodes more than others. Therefore, the visualisation of correlated nodes was done. However, for the offer prices the clear separation of correlated and not correlated nodes was not obtained. Finally, it was concluded that location factor most strongly affects correlation of electricity nodal prices; problems in visualisation probably associated with power losses when the power is transmitted over long distance.

Korkeapainevesisumusuuttimen virtaustekninen laadunhallinta

Tämä työ vastaa tarpeeseen hallita korkeapainevesisumusuuttimen laatua virtausmekaniikan työkalujen avulla. Työssä tutkitaan suutinten testidatan lisäksi virtauksen käyttäytymistä suuttimen sisällä CFD-laskennan avulla. Virtausmallinnus tehdään Navier-Stokes –pohjaisella laskentamenetelmällä. Työn teoriaosassa käsitellään virtaustekniikkaa ja sen kehitystä yleisesti. Lisäksi esitetään suuttimen laskennassa käytettävää perusteoriaa sekä teknisiä ratkaisuja. Teoriaosassa käydään myös läpi laskennalliseen virtausmekaniikkaan (CFD-laskenta) liittyvää perusteoriaa. Tutkimusosiossa esitetään käsitellyt suutintestitulokset sekä mallinnetaan suutinvirtausta ajasta riippumattomaan virtauslaskentaan perustuvalla laskentamenetelmällä. Virtauslaskennassa käytetään OpenFOAM-laskentaohjelmiston SIMPLE-virtausratkaisijaa sekä k-omega SST –turbulenssimallia. Tehtiin virtausmallinnus kaikilla paineilla, joita suuttimen testauksessa myös todellisuudessa käytetään. Lisäksi selvitettiin mahdolliset kavitaatiokohdat suuttimessa ja suunniteltiin kavitaatiota ehkäisevä suutingeometria. Todettiin myös lämpötilan ja epäpuhtauksien vaikuttavan kavitaatioon sekä mallinnettiin lämpötilan vaikutusta. Luotiin malli, jolla suuttimen suunnitteluun liittyviin haasteisiin voidaan vastata numeerisella laskennalla.

Securin, Cdc20 and Cdc27 in predicting the outcome of human breast cancer

Deregulated proliferation has been recognized among the most important factors promoting breast cancer development and progression. The aim of the project is to gain understanding of the role of specific cell cycle regulators of metaphase-anaphase transition and evaluate their potential in breast cancer prognostication and treatment decisions. Metaphase-anaphase transition is triggered by activation of anaphase promoting complex (APC) which is activated by a cascade of regulatory proteins, among them securin, Cdc20 and Cdc27. These proteins promote the metaphase–anaphase transition and participate in the timely separation of the chromatids. This study is based on a patient material of approximately 600 breast cancer patients and up to 22 years of follow-up. As the main observation, based on DNA cytometric and immunohistochemical methods, securin, Cdc20 and Cdc27 protein expressions were associated with abnormal DNA content and outcome of breast cancer. In the studied patient material, high securin expression alone and in combination with Cdc20 and Cdc27 predicted up to 9.8-fold odds for aneuploid DNA content in human breast cancer. In Kaplan–Meier analyses, high expression of securin systematically indicated decrease in breast cancer survival as compared to low expression cases. The adverse effect of high securin expression was further strengthened by combining it with Cdc20 or Cdc27 expressions, resulting in up to 6.8-fold risk of breast cancer death. High securin and Cdc20 expression was also associated with triple-negative breast cancer type with high statistical significance. Securin, Cdc20 or Cdc27 have not previously been investigated in a clinically relevant large breast cancer patient material or in association with DNA ploidy. The present findings suggest that the studied proteins may serve as potential biomarkers for identification of aggressive course of disease and unfavourable outcome of human breast cancer, and that they may provide a future research aim for understanding abnormal proliferation in malignant disease.

Requisites for a successful implementation of an automated inventory replenishment system

Tutkimuksen tavoitteena oli selvittää automaattisten tilausjärjestelmien onnistuneen käyttöönottoon taustalla vaikuttavia tekijöitä vähittäiskaupan toimialalla ja etsiä ratkaisua kyseisten järjestelmien onnistuneeseen käyttöönottoon tässä ympäristössä. Tutkimus analysoi yli sadan kaupan järjestelmän käyttöönottoa ja käyttöönoton tuloksia. Tutkimusta varten haastateltiin niin yhtiön sisältä kuin ulkopuoleltakin mukana olleita hankintajärjestelmän ja jalkautuksen asiantuntijoita. Tämän lisäksi järjestelmän käyttöönottaneisiin kauppoihin lähetettiin kyselyt, joita analysoitiin ryhmissä automaattisen tilausjärjestelmän tietojen pohjalta. Työn tuloksena pystyttiin tunnistamaan tietty joukko taustatekijöitä, jotka tulee ottaa käyttöönotossa huomioon sekä saatuihin tutkimustuloksiin perustuen kehitettiin malli vastaavanlaisten järjestelmien käyttöönotolle vähittäiskaupan alalle.