Modeling of fireside deposit formation in two industrial furnaces

Fireside deposits can be found in many types of utility and industrial furnaces. The deposits in furnaces are problematic because they can reduce heat transfer, block gas paths and cause corrosion. To tackle these problems, it is vital to estimate the influence of deposits on heat transfer, to minimize deposit formation and to optimize deposit removal. It is beneficial to have a good understanding of the mechanisms of fireside deposit formation. Numerical modeling is a powerful tool for investigating the heat transfer in furnaces, and it can provide valuable information for understanding the mechanisms of deposit formation. In addition, a sub-model of deposit formation is generally an essential part of a comprehensive furnace model. This work investigates two specific processes of fireside deposit formation in two industrial furnaces. The first process is the slagging wall found in furnaces with molten deposits running on the wall. A slagging wall model is developed to take into account the two-layer structure of the deposits. With the slagging wall model, the thickness and the surface temperature of the molten deposit layer can be calculated. The slagging wall model is used to predict the surface temperature and the heat transfer to a specific section of a super-heater tube panel with the boundary condition obtained from a Kraft recovery furnace model. The slagging wall model is also incorporated into the computational fluid dynamics (CFD)-based Kraft recovery furnace model and applied on the lower furnace walls. The implementation of the slagging wall model includes a grid simplification scheme. The wall surface temperature calculated with the slagging wall model is used as the heat transfer boundary condition. Simulation of a Kraft recovery furnace is performed, and it is compared with two other cases and measurements. In the two other cases, a uniform wall surface temperature and a wall surface temperature calculated with a char bed burning model are used as the heat transfer boundary conditions. In this particular furnace, the wall surface temperatures from the three cases are similar and are in the correct range of the measurements. Nevertheless, the wall surface temperature profiles with the slagging wall model and the char bed burning model are different because the deposits are represented differently in the two models. In addition, the slagging wall model is proven to be computationally efficient. The second process is deposit formation due to thermophoresis of fine particles to the heat transfer surface. This process is considered in the simulation of a heat recovery boiler of the flash smelting process. In order to determine if the small dust particles stay on the wall, a criterion based on the analysis of forces acting on the particle is applied. Time-dependent simulation of deposit formation in the heat recovery boiler is carried out and the influence of deposits on heat transfer is investigated. The locations prone to deposit formation are also identified in the heat recovery boiler. Modeling of the two processes in the two industrial furnaces enhances the overall understanding of the processes. The sub-models developed in this work can be applied in other similar deposit formation processes with carefully-defined boundary conditions.

Determinants of Polylepis (Rosaceae) Forest Distribution and Treeline Formation in the High Andes

High elevation treelines are formed under common temperature conditions worldwide, but the functional mechanisms that ultimately constrain tree growth are poorly known. In addition to environmental constraints, the distribution of high elevation forests is largely affected by human influence. Andean Polylepis (Rosaceae) forests are an example of such a case, forests commonly growing in isolated stands disconnected from the lower elevation montane forests. There has been ample discussion as to the role of environmental versus anthropogenic causes of this fragmented distribution of Polylepis forests, but the importance of different factors is still unclear. In this thesis, I studied functional, environmental and anthropogenic aspects determining Polylepis forest distribution. Specifically, I assessed the degree of genetic determinism in the functional traits that enable Polylepis species to grow in cold and dry conditions. I also studied the role of environment and human influence constraining Polylepis forest distribution. I found evidence of genetically determined climatic adaptations in the functional traits of Polylepis. High elevation species had reduced leaf size and increased root tip abundance compared to low elevation species. Thus these traits have potentially played an important role in species evolution and adaptation to high elevation habitats, especially to low temperatures. I also found reduced photosynthesis rate among high elevation tree species compared to low elevation species, supporting carbon source limitation at treelines. At low elevations, Polylepis forest distribution appeared to be largely defined by human influence. This suggests that the absence of Polylepis forests in large areas in the Andes is the result of several environmental and anthropogenic constraints, the role of environment becoming stronger towards high elevations. I also show that Polylepis trees grow at remarkably low air and soil temperatures near treelines, and present new evidence of the role of air temperatures in constraining tree growth at high elevations. I further show that easily measurable indices of accessibility are related to the degree of degradation of Polylepis forest, and can therefore be used in the rapid identification of potentially degraded Polylepis forests. This is of great importance for the conservation and restoration planning of Polylepis forests in the Andes. In a global context, the results of this thesis add to our scientific knowledge concerning high elevation adaptations in trees, and increase our understanding of the factors constraining tree growth and forest distribution at high-­elevation treelines worldwide.

Oxalic acid and calcium oxalate in production of wood-containing paper : formation, analysis, and control

Papperstillverkningen störs ofta av oönskade föreningar som kan bilda avsättningar på processytor, vilket i sin tur kan ge upphov till störningar i pappersproduktionen samt försämring av papperskvaliteten. Förutom avsättningar av vedharts är stenliknande avlagringar av svårlösliga salter vanliga. I vårt dagliga liv är kalkavlagringar i kaffe- och vattenkokare exempel på liknande problem. I massa- och pappersindustrin är en av de mest problematiska föreningarna kalciumoxalat; detta salt är nästan olösligt i vatten och avlagringarna är mycket svåra att avlägsna. Kalciumoxalat är också känt som en av orsakerna till njurstenar hos människor. Veden och speciellt barken innehåller alltid en viss mängd oxalat men en större källa är oxalsyra som bildas när massan bleks med oxiderande kemikalier, t.ex. väteperoxid. Kalciumoxalat bildas när oxalsyran reagerar med kalcium som kommer in i processen med råvattnet, veden eller olika tillsatsmedel. I denna avhandling undersöktes faktorer som påverkar bildningen av oxalsyra och utfällningen av kalciumoxalat, med hjälp av bleknings- och utfällningsexperiment. Forskningens fokus låg speciellt på olika sätt att förebygga uppkomsten av avlagringar vid tillverkning av trähaltigt papper. Resultaten i denna avhandling visar att bildningen av oxalsyra samt utfällning av kalciumoxalat kan påverkas genom processtekniska och våtändskemiska metoder. Noggrann avbarkning av veden, kontrollerade förhållanden under den alkaliska peroxidblekningen, noggrann hantering och kontroll av andra lösta och kolloidala substanser, samt utnyttjande av skräddarsydd kemi för kontroll av avlagringar är nyckelfaktorer. Resultaten kan utnyttjas då man planerar blekningssekvenser för olika massor samt för att lösa problem orsakade av kalciumoxalat. Forskningsmetoderna som användes i utfällningsstudierna samt för utvärdering av tillsatsmedel kan också utnyttjas inom andra områden, t.ex. bryggeri- och sockerindustrin, där kalciumoxalatproblem är vanligt förekommande. -------------------------------------------- Paperinvalmistusta häiritsevät usein erilaiset epäpuhtaudet, jotka kiinnittyvät prosessipinnoille ja haittaavat tuotantoa sekä paperin laatua. Puun pihkan lisäksi eräs yleinen ongelma on niukkaliukoisten suolojen aiheuttamat kivettymät. Kalkkisaostuma kahvinkeittimessä on esimerkki vastaavasta ongelmasta arkielämässä. Massa- ja paperiteollisuudessa yksi hankalimmista kivettymien muodostajista on kalsiumoksalaatti, koska se on lähes liukenematonta ja sen aiheuttamat saostumat ovat erittäin vaikeasti poistettavia. Kalsiumoksalaatti on yleisesti tunnettu myös munuaiskivien aiheuttajana ihmisillä. Puu ja varsinkin sen kuori sisältää aina jonkin verran oksalaattia, mutta suurempi lähde on kuitenkin oksaalihappo jota muodostuu valkaistaessa massaa hapettavilla kemikaaleilla, kuten vetyperoksidilla. Kalsiumoksalaattia syntyy kun veden, puun ja lisäaineiden mukana prosessiin tuleva kalsium reagoi oksalaatin kanssa. Tässä väitöskirjatyössä tutkittiin oksaalihapon muodostumiseen ja kalsiumoksalaatin saostumiseen vaikuttavia tekijöitä valkaisu- ja saostumiskokeiden avulla. Tutkimuksen painopiste oli saostumien ehkäisemisessä puupitoisten painopaperien valmistuksessa. Työssä saadut tulokset osoittavat että oksaalihapon muodostumiseen ja kalsiumoksalaatin saostumiseen voidaan vaikuttaa sekä prosessiteknisten että märänpään kemian keinojen avulla. Tehokas puun kuorinta, optimoidut olosuhteet peroksidivalkaisussa, muiden liuenneiden ja kolloidisten aineiden hallinta sekä räätälöidyn kemian hyödyntäminen kalsiumoksalaattisaostumien torjunnassa ovat keskeisissä rooleissa ongelmien välttämiseksi. Väitöskirjatyön tuloksia voidaan hyödyntää massan valkaisulinjoja suunniteltaessa sekä kalsiumoksalaatin aiheuttamien ongelmien ratkaisemisessa. Tutkimusmenetelmiä, joita käytettiin saostumiskokeissa ja eri lisäaineiden vaikutusten arvioinnissa, voidaan hyödyntää massa- ja paperiteollisuuden lisäksi myös muilla alueilla, kuten sokeri- ja panimoteollisuudessa, joissa ongelma on myös yleinen.

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.

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.