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.

Together Everyone Achieves More? Herding Behavior in the Finnish Stock Market

This thesis examines whether or not Finnish stock markets has herding behavior. Sample data is from 2004 to 2013. Including total of 2516 market days. Market wide herding, up and down market herding, extreme price movement herding and turnover volume herding are measured in this thesis. Methods used in this thesis are cross-sectional absolute dispersion and cross-sectional standard deviation. This thesis found no signs of herding in the Finnish stock market.

Forecasting financial weather - can we foresee market sentiment? Spectrum of stock price behavior - NYSE case study

The desire to create a statistical or mathematical model, which would allow predicting the future changes in stock prices, was born many years ago. Economists and mathematicians are trying to solve this task by applying statistical analysis and physical laws, but there are still no satisfactory results. The main reason for this is that a stock exchange is a non-stationary, unstable and complex system, which is influenced by many factors. In this thesis the New York Stock Exchange was considered as the system to be explored. A topological analysis, basic statistical tools and singular value decomposition were conducted for understanding the behavior of the market. Two methods for normalization of initial daily closure prices by Dow Jones and S&P500 were introduced and applied for further analysis. As a result, some unexpected features were identified, such as a shape of distribution of correlation matrix, a bulk of which is shifted to the right hand side with respect to zero. Also non-ergodicity of NYSE was confirmed graphically. It was shown, that singular vectors differ from each other by a constant factor. There are for certain results no clear conclusions from this work, but it creates a good basis for the further analysis of market topology.

Hygro-elasto-plastic behavior of planar orthotropic material

The mechanical and hygroscopic properties of paper and board are factors affecting the whole lifecycle of a product, including paper/board quality, production, converting, and material and energy savings. The progress of shrinkage profiles, loose edges of web, baggy web causing wrinkling and misregistration in printing are examples of factors affecting runnability and end product quality in the drying section and converting processes, where paper or board is treated as a moving web. The structural properties and internal stresses or plastic strain differences built up during production also cause the end-product defects related to distortion of the shape of the product such as sheet or box. The objective of this work was to construct a model capable of capturing the characteristic behavior of hygroscopic orthotropic material under moisture change, during different external in-plane stretch or stress conditions. Two independent experimental models were constructed: the elasto-plastic material model and the hygroexpansivity-shrinkage model. Both describe the structural properties of the sheet with a fiber orientation probability distribution, and both are functions of the dry solids content and fiber orientation anisotropy index. The anisotropy index, introduced in this work, simplifies the procedure of determining the constitutive parameters of the material model and the hygroexpansion coefficients in different in-plane directions of the orthotropic sheet. The mathematically consistent elasto-plastic material model and the dry solids content dependent hygroexpansivity have been constructed over the entire range from wet to dry. The presented elastoplastic and hygroexpansivity-shrinkage models can be used in an analytical approach to estimate the plastic strain and shrinkage in simple one-dimensional cases. For studies of the combined and more complicated effects of hygro-elasto-plastic behavior, both models were implemented in a finite element program for a numerical solution. The finite element approach also offered possibilities for studying different structural variations of orthotropic planar material, as well as local buckling behavior and internal stress situations of the sheet or web generated by local strain differences. A comparison of the simulation examples presented in this work to results published earlier confirms that the hygro-elasto-plastic model provides at least qualitatively reasonable estimates. The application potential of the hygro-elasto-plastic model is versatile, including several phenomena and defects appearing in the drying, converting and end-use conditions of the paper or board webs and products, or in other corresponding complex planar materials.

Permanent magnet synchronous generator design solution for large directdrive wind turbines: Thermal behavior of the LC DD-PMSG

Wind is one of the most compelling forms of indirect solar energy. Available now, the conversion of wind power into electricity is and will continue to be an important element of energy self-sufficiency planning. This paper is one in a series intended to report on the development of a new type of generator for wind energy; a compact, high-power, direct-drive permanent magnet synchronous generator (DD-PMSG) that uses direct liquid cooling (LC) of the stator windings to manage Joule heating losses. The main param-eters of the subject LC DD-PMSG are 8 MW, 3.3 kV, and 11 Hz. The stator winding is cooled directly by deionized water, which flows through the continuous hollow conductor of each stator tooth-coil winding. The design of the machine is to a large degree subordinate to the use of these solid-copper tooth-coils. Both steady-state and timedependent temperature distributions for LC DD-PMSG were examined with calculations based on a lumpedparameter thermal model, which makes it possible to account for uneven heat loss distribution in the stator conductors and the conductor cooling system. Transient calculations reveal the copper winding temperature distribution for an example duty cycle during variable-speed wind turbine operation. The cooling performance of the liquid cooled tooth-coil design was predicted via finite element analysis. An instrumented cooling loop featuring a pair of LC tooth-coils embedded in a lamination stack was built and laboratory tested to verify the analytical model. Predicted and measured results were in agreement, confirming the predicted satisfactory operation of the LC DD-PMSG cooling technology approach as a whole.

Psychological well-being of the parents and child development, behavior, and quality of life in very low birth weight infants

The parents of premature infants, especially the mothers, are at increased risk for distress. Infants born prematurely are at risk for developmental problems. The aim of this study was to investigate whether the psychological well-being of both parents is associated with child development in very low birth weight (VLBW, ≤1500g) children. The burden of prematurity-related morbidity to the children and to the family was also assessed. A cohort of 201 VLBW infants born during 2001–2006 in the Turku University Hospital, Finland, and their parents were studied (I–IV). One study included a control group (n=166) of full-term infants (IV). The psychological well-being of the parents was evaluated by assessments of depressive symptoms, parenting stress, the sense of coherence and general family functioning. Cognitive, behavioral, and socio-emotional development, and the health-related quality of life (HRQoL) of the children were determined when the children were 2 to 8 years old. The psychological well-being of the parents was associated with the cognitive, behavioral and social development of the VLBW children. The VLBW infants with prematurity-related morbidities had a poorer HRQoL and the general functioning of the family was inferior compared to the control children and their families. 64.5% of the VLBW children survived without morbidities. Most of the VLBW children did not have significant behavior problems (93%), had normal social skills (63%), had no emotional problems (64%), and had no problems in executive functioning (62%). Only 3% of the surviving VLBW infants had significant cognitive delay. In conclusion, the depressive symptoms and stress of the parents can be risk factors for disadvantageous child development, while a strong sense of coherence can be protective. Parents of the premature children with developmental delays might also experience more depressive symptoms and stress than other parents. Prematurity-related morbidities were a burden to the VLBW child as well as to the family.

Explaining the intention to play and behavior of playing sports betting games of young Finnish adults : an application of the theory of planned behavior

The aim of this Master’s Thesis was to examine the determinants of intention and behavior of playing sports betting games in order to explain the intention to play in a more precise way and to be able to understand the behavior of playing. The theory of planned behavior was applied in explaining the intention of young Finnish adults aged 18 to 34. A quantitative research method was applied and an online survey was sent to the students of Lappeenranta University of Technology and to the subscribers of Urheilulehti in order to reach a sample that present the young population of Finland. The theory of the study focused on the theory of planned behavior and its antecedents, attitude towards behavior, subjective norms, perceived behavioral control as well as motivation. By analyzing the data, causal relationships were found through which the explanation of intention was possible. The results showed that attitude towards playing, subjective norms, perceived behavioral control and motivation impact the formation of intention significantly. The results also indicated that intention impacts significantly to the playing frequency.

Effects of Fabrication Processes on the Behavior of S960 Ultra High Strength Steel (UHSS)

Strenx® 960 MC is a direct quenched type of Ultra High Strength Steel (UHSS) with low carbon content. Although this material combines high strength and good ductility, it is highly sensitive towards fabrication processes. The presence of stress concentration due to structural discontinuity or notch will highlight the role of these fabrication effects on the deformation capacity of the material. Due to this, a series of tensile tests are done on both pure base material (BM) and when it has been subjected to Heat Input (HI) and Cold Forming (CF). The surface of the material was dressed by laser beam with a certain speed to study the effect of HI while the CF is done by bending the specimen to a certain angle prior to tensile test. The generated results illustrate the impact of these processes on the deformation capacity of the material, specially, when the material has HI experience due to welding or similar processes. In order to compare the results with those of numerical simulation, LS-DYNA explicit commercial package has been utilized. The generated results show an acceptable agreement between experimental and numerical simulation outcomes.

Metrics for Predicting User Behavior and Experience in an Interactive Storytelling System

In much of the previous research into the field of interactive storytelling, the focus has been on the creation of complete systems, then evaluating the performance of those systems based on user experience. Less focus has been placed on finding general solutions to problems that manifest in many different types of interactive storytelling systems. The goal of this thesis was to identify potential candidates for metrics that a system could use to predict player behavior or how players experience the story they are presented with, and to put these metrics to an empirical test. The three metrics that were used were morality, relationships and conflict. The game used for user testing of the metrics, Regicide is an interactive storytelling experience that was created in conjunction with Eero Itkonen. Data, in the forms of internal system data and survey answers, collected through user testing, was used to evaluate hypotheses for each metric. Out of the three chosen metrics, morality performed the best in this study. Though further research and refinement may be required, the results were promising, and point to the conclusion that user responses to questions of morality are a strong predictor for their choices in similar situations later on in the course of an interactive story. A similar examination for user relationships with other characters in the story did not produce promising results, but several problems were recognized in terms of methodology and further research with a better optimized system may yield different results. On the subject of conflict, several aspects, proposed by Ware et al. (2012), were evaluated separately. Results were inconclusive, with the aspect of directness showing the most promise.

Facilitating corporate entrepreneurial behavior: A study of corporate entrepreneurial behavior in corporate banking

This study discusses the pronounced importance of corporate entrepreneurial behavior, CEB, facilitation and enablement as a key dimension in the rapidly changing business environment within companies. The research target is a large finance company in Finland, where regulations, compliance and processes restrict and refine extensively business approach. The purpose of this study is to foster the understanding of corporate entrepreneurial behavior and requirements and identify the supporters and inhibitors of facilitation of it. Furthermore, this study examines who should be driving the implementation and offer concrete outcome for the company to get the facilitation started and berth it as part of the organizational culture and values. The theoretical background is constructed from literature related to concept of corporate entrepreneurial behavior, factors supporting and hindering the facilitation based on previous studies and innovation management. Furthermore theoretical framework of middle managers entrepreneurial behavior in facilitation process was researched. Additionally top down and bottom up approach of conversational space building within the organization in order to foster innovation and involving mindset and behavior was in the core literature. The empirical research conducted for the study consists three parts; innovation audit questionnaire, semi-structured interviews and secondary data from previously made research within the case company. Questionnaire and interviews were targeted to eight middle managers within the company, the head of branch regions in corporate segment. The secondary data was collected from over 300 employees in the case company by an external company. Research results were analyzed mainly by themes and source division in adaption with the theoretical framework. The study finds that facilitation of CEB should be a strategic choice and requires strong management support and examples. Behavior should be involved with organizational culture, values, structures and processes. The companies´ willingness to take risks and encourage employees at all levels to participate and be involved by taking ownership and responsibility is in the core. CEB is found to be a key dimension in increasing employee satisfaction and engagement, competitive advantages and economic growth of companies. There is increased interest towards CEB in the case company but there is lack in the mutual consensus of it. CEB is not in the strategy although the mindset and support from management is in place. There is no concrete enablement and space for innovation and CEB although the platform would be receptive. Further research is needed to build shared vision of CEB and how to make it a part of the organizational culture and values in addition to building the conversational space.

Corporate Entrepreneurship in Healthcare Organizations: An explorative study of employees’ corporate entrepreneurial behavior, job satisfaction and turnover intention

The Finnish healthcare industry is currently facing significant challenges due to economic crises, aging population and major structural reforms, which have resulted in decreased job satisfaction and increased levels of turnover. This proposes that healthcare organizations need to come up with new, creative means to tackle these issues. Several researchers have argued that corporate entrepreneurship may be the necessary means to achieve this. As previous research has mainly focused on examining this concept from organizational perspective, this study looks at how it occurs on the level of individual employees. The purpose of this study is to examine how corporate entrepreneurship is manifested in individual behavior, and how this type of behavior is associated with the individual’s job satisfaction and turnover intention. Additionally, this study will examine the differences in corporate entrepreneurial behavior between private and public sector organizations, as previous research suggests that these two may be characterized differently. Data was collected with the help of a literature review as well as a survey study, which was sent out to a number of employees of four different healthcare organizations, out of which three were public and one was a private sector organization. Six distinct behavioral characteristics were recognized in previous research, which make up the measure for corporate entrepreneurial behavior. Principal components were formed from the different areas of the survey (corporate entrepreneurial behavior, job satisfaction, turnover intention), after which the association of these components were examined with linear regression analysis, which proved that corporate entrepreneurial behavior is positively correlated with both job satisfaction and intention to leave the organization. Differences between sectors were analyzed with analysis of variance and cross tabulation analysis, but neither of these suggested that any significant differences would occur. These results suggest that employees who behave entrepreneurially tend to be more satisfied with their jobs, but also consider leaving their current organizations more often than others. This may be due to the fact that healthcare organizations are not fertile for entrepreneurial behavior, which will drive entrepreneurial individuals looking for employers who may be more supportive of this type of behavior. With growing levels of dissatisfaction as well as little room for entrepreneurial behavior, the studied organizations may actually be in the process of losing those employees who have the ability and desire to behave in such manner, and who could very well be those who will eventually come up with solutions for the major challenges that these organizations are facing.

Consumer Behavior in Mortgage Market: Evidence from Russia

The purpose of this master thesis is to identify behavioral patterns of potential borrower in mortgage market in crisis conditions and to link mortgage products available on Russian market with potential borrowers segments in dependence of detected patterns. Empirical results achieved through 172 answers of potential borrowers allowed to classify them in four groups in dependence of respondent perceptions about mortgage and future. On the basis of literature review and currently state of Russian mortgage market particular mortgage products were suggested to each of four clusters of potential borrowers. Then, recommendations for Russian banks how to apply received results were developed. Current master thesis has strong both academic and managerial contributions. It it adds significant value to existing consumer behavior studies; and provides practical recommendations for Russian banks how to understand mortgage borrower behavior in order to increase trust to mortgage among population.