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.

Formation of nitrates in water in presence of formate and oxalate treated with pulsed corona discharge (PCD)

Tavallisten hapetusmenetelmien sijasta kehittyneitä hapetusmenetelmiä (AOP) on kehitetty yhä enemmän, jotta hapetusprosessista tulisi kannattavampi, tehokkaampi, ympäristöystävällisempi ja sitä voitaisiin hyödyntää laajalti eri paikoissa. Uusi teknologia, joka käyttää otsonia ja hydroksyyliradikaalia sähköimpulssien kanssa, on yksi mahdollinen tehokkaampi vedenkäsittelymentelmä. Kyseistä menetelmää kutsutaa pulsed corona discharge (PCD) -menetelmäksi, joka käyttää prosessissa muodostuvia otsonia ja hydroksyyliradikaalia hapettavina tekijöinä. Tässä työssä tutkittiin nitraatin muodostumista vedessä, kun vettä käsiteltiin PCD-laitteessa ja, kun oksalaatti- ja formaatti-ioneja oli sekoittuneina veteen. Nitraatteja muodostuu PCD–laitteessa veteen, kun ilman typpi reagoi hapettimina toimivien otsonin ja hydroksyyliradikaalin kanssa. Aiemmissa tutkimuksissa nitraatin muodostumisen on todistettu parantuvan, kun karboksyylihapot muurahais- ja oksaalihappo ovat sekoittuneina veteen. Tässä tutkimuksessa tarkoituksena oli tutkia, miten formaatti- ja oksalaatti-ionien, joiden pitoisuudet olivat 0 ppm, 50 ppm ja 100 ppm, läsnäolo vedessä vaikuttaa nitraatin muodostumiseen. PCD-kokeista saadut näytteet analysoitiin ionikromatografilla. Kyseisessä tutkimuksessa nitraatin muodostuminen oli samansuuruista jokaisessa kokeessa hapetusajan kasvaessa samalla, kun otettujen näytteiden pH-arvot laskivat. Tuloksena voitiin pitää sitä, ettei formaatti- tai oksalaatti-ioneilla ollut vaikutusta nitraatti-ionien muodostumiseen.

The best practices in the formation phase of Sino-Finnish joint ventures in China: For Finnish software companies

This study discusses the formation phase of Chinese-Finnish joint ventures in China. The purpose of this thesis is to create best practices for Finnish software companies in forming a joint venture with a local Chinese company in China. Therefore, the main research question, in what are the best practices for forming Sino-Finnish joint ventures in China for Finnish software firms, is examined through four different themes within the joint venture formation phase; the motives, the partner se- lection, the choice of a joint venture type and joint venture negotiations. The theoretical background of the study consists of literature relating to the establishment process of Sino-Western joint ventures in China. The empirical research conducted for this study is based on the expert interviews. The empirical data was gathered via nine semi-structured interviews with both Chinese and Finnish experts in software and technology industry, who have experience or knowledge in establishing Sino-Finnish joint ventures in China. Thematic analysis was used to cat- egorize and interpret the interview data. In addition, a thematic network was built to act as a basis of the analysis. According to the main findings, the main motives for Finnish software companies to establish a joint venture in China are lack of skills or experience, little resources to enter on their own, and China’s large market. The main motives for Chinese companies are to gain new technology or man- agerial skills, and expand internationally. The intellectual property rights (IPR) have recently im- proved a lot in China, but the Finnish companies’ knowledge on IPR is inadequate. The Finnish software companies should conduct a market and industry research in order to understand their po- sition in the market and to find a suitable location and potential joint venture partners. It is essential to define partner selection criteria and partner attributes. In addition, it is important to build the joint venture around complementary motives and a win-win situation between the joint venture partners. The Finnish companies should be prepared that the joint venture negotiations will be challenging and they will take a long time. The challenges can be overcome by gaining understanding about the Chinese culture and business environment. The findings of this study enhance understanding of the joint venture formation phase in China. This study provides guidelines for Finnish software companies to establish a joint venture in China. In addition, this study brings new insights to the Sino-Western joint venture literature with its soft- ware industry context. Future research is, however, necessary in order to gain an understanding of the advantages and disadvantages of a joint venture as an entry mode into China for Finnish soft- ware companies

The Formation Of Internationalization Strategies Within The Construction Industry:Vision and Strategy

Internationalization represents a complex topic that has been researched for quite some time. However, since it continues to be extremely current a topic, its significance has not diminished, but maybe even increased in importance. Companies today face extreme pressure to enter new markets in the hope of growing, becoming more profitable, increasing market share, attracting new customers and meeting the requirements of its share- and stakeholders. In the increasingly global business environment of today, companies are facing both challenges and possible advantages of internationalization. Few companies are not operating internationally and it is becoming the question of ‘Why not?’ rather than ‘Why?’ to internationalize business operations. Internationalization and the importance of strategy are discussed in this research from the viewpoint of three case companies that were interviewed about internationalization strategies. This research project is a qualitative study that answers the research question of How is a business strategy constructed for entering a new market? The sub-questions are • How are goals set and what indicators are used to monitor the achievement of these goals? • What are the key characteristics of a strategy implementation process? The research method chosen for this study is a multiple-case study. Three case companies were chosen for the interviews in order to gain in-depth data of internationalization strategies within the construction industry.

Formation of the Employer Brand Image

The purpose of this study was to explore the employer brand image and its formation of a Finnish (yet international) service company in B2B sector. In the research qualitative case study method was used to explore the most preferred attributes in employer attraction, the employer brand perceptions towards the case company, and the effectors behind these brand perceptions among the prospective group of employees. The research was conducted through in-depth semistructured interviews among 23-30 undergraduate or graduate business students in Finnish universities close to their graduation. After deriving the attributes of an attractive employer, and exploring their relation to the case company, the employer brand image of the case company was determined and its attractiveness level evaluated. Moreover, the formation of the employer brand image was investigated and its sources detected. The most important factors for the target group in employer attractiveness were found to be company reputation and company culture/work atmosphere. Also career opportunities and international opportunities were seen important. The case company was found to hold a positive, attractive image on company culture and international opportunities, but failing to hold a good reputation as a fair employer. The main and most impactful source of employer brand image was former and current employees - directly or indirectly. Company’s own actions played only small part in employer brand formation as credibility is a critical factor in brand image formation and corporate communication found not to be perceived genuine. Based on the findings, suggestions for further employer branding were made.

Ethical leadership as a way to promote work-related well-being

The purpose of this study was to clarify the connections of ethical leadership with the work-related well-being of employees. Additionally, the role of occupational health care in ethical leadership that promotes work-related well- being was analyzed. The objective of the study was to produce knowledge to support the development of ethical leadership and work-related well-being as well as to find ways for occupational health care to support organizations in these actions. The target groups of this study consisted of the managers (N=43) and employees (N=336) working in one organization in the Finnish energy industry. The population was studied in November 2014 using census. The data was gathered with two different web-based surveys containing structured and open questions. The survey for managers consisted of background questions and statements concerning ethical leadership, work-related well-being and occupational health care. The employee questionnaire consisted of questions about background and statements about work-related well-being and ethical leadership. The structured questions were analyzed with SPSS Statistical Program and the open questions using inductive content analysis. At least 80 % of the managers saw their actions as ethical in all but one part of ethical leadership. The work-related well-being of the employees was found best in the area of ability to work (91 % agreed) and lowest in the area of experience of ethical leadership (67 % agreed). The results showed a strong positive connection between ethical leadership and all the components of work- related well-being. The managers and employees were generally quite happy with the services of occupational health care but managers saw some problems with the collaboration with occupational health care. Several ways to improve work-related well-being and collaboration with occupational health care were found. One of the most important things was thought to be offering ways to maintain ability to work and making these actions visible. Investing in ethical leadership and work-related well-being is extremely important for the success of an organization and the societal benefits cannot be forgotten either. The role of occupational health care in promoting the health and well-being of employees is substantial. Occupational health care should offer managers more tools to recognize difficult situations and acting in them as well as encourage managers to seek help from occupational health care without hesitation in problematic situations of leadership.

Bacterial adhesion and biofilm formation on monolithic zirconia

Tutkimuksen tavoitteena oli selvittää bakteerien kiinnittymistä ja bakteeribiofilmin muodostumista implanttimateriaalien pinnalla. Monoliittisen zirkonian ja lasikeramien käyttö implanttikruunujen materiaaleina kasvaa jatkuvasti. Zirkoniaa käytetään myös abutmenttien materiaalina esteettisillä alueilla. Tällä hetkellä on vain vähän tutkimustietoa näiden implanttikruunumateriaalien sekä implanttikruunujen sementoimiseen käytetyn sementin pinnalla tapahtuvasta bakteeriadheesiosta ja biofilmin muodostumisesta. Bakteerien adheesiota ja biofilmin muodistumista tutkittiin neljän eri materiaalin pinnalla. Tutkimuksessa käytetyt materiaalit olivat: (1) Litiumdisilikaatti (LDS; IPS e.max CAD, Ivoclar Vivadent,kontrolli), (2) Kokonaan stabiloitu zirkonia (FSZ; Prettau Anterior, Zirkonzahn), (3) Osittain stabiloitu zirkonia (PSZ; Katana, Noritake), ja (4) Kaksoiskovetteinen sementti (DCC; Multilink hybrid abutment cement, Ivoclar Vivadent). Kaikki tutkimuksessa käytetyt materiaalit valmisteltiin ja kiillotettiin valmistajien ohjeiden mukaisesti Tutkittavat pinnat inkuboitiin Streptococcus mutans-suspensiossa +37°C:ssä asteessa. Bakteeriadheesiotestissä inkubointiaika oli 30 minuuttia ja biofilmitestissä vastaava aika oli 24 tuntia. Materiaalien pintoja tarkasteltiin myös elektronimikroskooppia käyttäen. Tutkimuksessa todettiin, että bakteeriadheesiossa oli eroja eri materiaalien välillä. Biofilmin. muodostumisessa ei todettu tilastollisesti merkittäviä eroja tutkittavien materiaalien välillä.

Consumer’s purchase intention of ethical fashion. Examining beliefs about fashion industry and attitudes towards ethical fashion

Globalization and the developments of supply chain have made inexpensive labor and the low production costs of developing countries available to businesses worldwide. Unfortunately, these developments have also led to the exploitation of human and natural resources. The increasing supply of cheap and fashionable clothing has created a contradiction between consumers’ concerns for sustainability and their purchase behavior in the fashion industry. Since the uncovering of several sweatshop scandals in the 1980’s and 1990’s ethical fashion brands have started to emerge. Ethical fashion has sparked the interest of consumers and studies have shown promising positive attitudes towards it. However, these attitudes have failed to translate into action and purchase behavior of ethical fashion has not reached the expectations. In order to translate the positive attitudes into buying companies must understand consumer’s motivations and reasons behind the purchase decision. The objective of this study is to understand the antecedents behind young consumer’s purchase intention of ethical fashion. The study is based on the theory of planned behavior which has been widely used to study consumer behavior and purchase decisions. The theory has also been used in ethical decision-making and fashion context before. According to the theory, in order to understand purchase intentions consumer’s attitudes toward buying ethical fashion were studied. The theory also states that attitudes are formed from beliefs, thus, consumer’s beliefs about the fashion industry were studied. To contribute to existing research, the effect of sweatshop issues and environmental issues were compared. The data was collected from university students (n=617) with an online survey. The results were analyzed by statistical methods and they revealed that young Finnish consumers hold positive attitudes towards buying ethical fashion as well as positive purchase intentions of ethical fashion. A strong relationship was found between positive attitudes and positive purchase intentions. Also, the more negative consumers’ beliefs of the fashion industry were the more positive their attitudes toward buying ethical fashion were. In contradiction to previous research this study revealed that environmental issues had greater effect on attitudes than sweatshop issues. Interesting differences between consumers were found depending on their field of education. Students from humanities and social sciences held the most negative beliefs as well as most positive attitudes and purchase intentions of ethical fashion.

The best practices in the formation phase of Sino-Finnish joint ventures in China: For Finnish software companies

This study discusses the formation phase of Chinese-Finnish joint ventures in China. The purpose of this thesis is to create best practices for Finnish software companies in forming a joint venture with a local Chinese company in China. Therefore, the main research question, in what are the best practices for forming Sino-Finnish joint ventures in China for Finnish software firms, is examined through four different themes within the joint venture formation phase; the motives, the partner se-lection, the choice of a joint venture type and joint venture negotiations. The theoretical background of the study consists of literature relating to the establishment process of Sino-Western joint ventures in China. The empirical research conducted for this study is based on the expert interviews. The empirical data was gathered via nine semi-structured interviews with both Chinese and Finnish experts in software and technology industry, who have experience or knowledge in establishing Sino-Finnish joint ventures in China. Thematic analysis was used to cat-egorize and interpret the interview data. In addition, a thematic network was built to act as a basis of the analysis. According to the main findings, the main motives for Finnish software companies to establish a joint venture in China are lack of skills or experience, little resources to enter on their own, and China’s large market. The main motives for Chinese companies are to gain new technology or man-agerial skills, and expand internationally. The intellectual property rights (IPR) have recently im-proved a lot in China, but the Finnish companies’ knowledge on IPR is inadequate. The Finnish software companies should conduct a market and industry research in order to understand their po-sition in the market and to find a suitable location and potential joint venture partners. It is essential to define partner selection criteria and partner attributes. In addition, it is important to build the joint venture around complementary motives and a win-win situation between the joint venture partners. The Finnish companies should be prepared that the joint venture negotiations will be challenging and they will take a long time. The challenges can be overcome by gaining understanding about the Chinese culture and business environment. The findings of this study enhance understanding of the joint venture formation phase in China. This study provides guidelines for Finnish software companies to establish a joint venture in China. In addition, this study brings new insights to the Sino-Western joint venture literature with its soft-ware industry context. Future research is, however, necessary in order to gain an understanding of the advantages and disadvantages of a joint venture as an entry mode into China for Finnish soft-ware companies.

Internal Employer Brand: The factors affecting the formation of internal employer image

The purpose of this study is to identify the factors affecting the formation of employer image and attractiveness in the minds of an organization’s employees. Six employees from different backgrounds and business units within a larger organization are interviewed, and the results are compared in order to better understand the effect divergent variables have on the resulting factors. The theoretical background of the research is based on the study of the concept of employer branding, an organization’s effort in affecting the employer image it projects and attractiveness perceived by the employees and applicants. The results of the study reveal how immaterial factors, primarily related to self-actualization and social relationships, often took precedence over material ones, so long as the material factors, such as salary and work equipment, were at least on a minimum level acceptable to the employee. As such, focusing on these immaterial factors when forming an employer brand strategy is expected to yield larger benefits in form of employer attractiveness.

Ethical leadership as a way to promote work-related well-being

The purpose of this study was to clarify the connections of ethical leadership with the work-related well-being of employees. Additionally, the role of occupational health care in ethical leadership that promotes work-related well- being was analyzed. The objective of the study was to produce knowledge to support the development of ethical leadership and work-related well-being as well as to find ways for occupational health care to support organizations in these actions. The target groups of this study consisted of the managers (N=43) and employees (N=336) working in one organization in the Finnish energy industry. The population was studied in November 2014 using census. The data was gathered with two different web-based surveys containing structured and open questions. The survey for managers consisted of background questions and statements concerning ethical leadership, work-related well-being and occupational health care. The employee questionnaire consisted of questions about background and statements about work-related well-being and ethical leadership. The structured questions were analyzed with SPSS Statistical Program and the open questions using inductive content analysis. At least 80 % of the managers saw their actions as ethical in all but one part of ethical leadership. The work-related well-being of the employees was found best in the area of ability to work (91 % agreed) and lowest in the area of experience of ethical leadership (67 % agreed). The results showed a strong positive connection between ethical leadership and all the components of work- related well-being. The managers and employees were generally quite happy with the services of occupational health care but managers saw some problems with the collaboration with occupational health care. Several ways to improve work-related well-being and collaboration with occupational health care were found. One of the most important things was thought to be offering ways to maintain ability to work and making these actions visible. Investing in ethical leadership and work-related well-being is extremely important for the success of an organization and the societal benefits cannot be forgotten either. The role of occupational health care in promoting the health and well-being of employees is substantial. Occupational health care should offer managers more tools to recognize difficult situations and acting in them as well as encourage managers to seek help from occupational health care without hesitation in problematic situations of leadership.