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.

Effects of alkaline fly ash precipitation on the Sphagnum mosses in Niinsaare bog, NE Estonia

Tiivistelmä: Emäksisen tuhkalaskeuman vaikutus rahkasammaliin Niinsaarensuolla Koillis-Virossa

The effects of alkaline fly ash precipitation on the Sphagnum mosses in Niinsaare bog, NE Estonia

Tiivistelmä: Emäksisen tuhkalaskeuman vaikutus rahkasammaliin Niinsaarensuolla Koillis-Virossa

Impact of precipitation on the water table level of different ombrotrophic raised bog complexes, central Estonia

Sadannan vaikutus vedenpinnan tasoon kohosuolla

U.S. landowner behavior, land use and land cover changes, and climate change mitigation

Abstract

In-line Monitoring of Precipitation Process using Raman Spectroscopy and ATR-FTIR

Polymorfian jatkuva seuranta saostuksessa on hyödyllistä suunnittelun ja kidetuotteen ominaisuuksien sekä kiteytystä seuraavan jatkoprosessoinnin kannalta. Tässä diplomityössä on tutkittu L-glutamiinihapon kahden (- ja ß) polymorfimuodon liukoisuuden riippuvuutta pH:sta ja lämpötilasta.Tulokseksi saatiin, että kummankin polymorfin liukoisuus kasvoi sekä pH:ta ettälämpötilaa kasvatettaessa. ¿¿muodon liukoisuus oli korkeampi kuin ß-muodon liukoisuus valituilla pH-arvoilla eri lämpötiloissa. Lisäksi seurattiin puolipanostoimisen saostuksen aikana 1-litraisella laboratoriokiteyttimellä muodostuvan kiteisen polymorfiseoksen koostumusta hyödyntäen in-line Raman-spektroskopiaa. Myös liuoksen pH-muutosta seurattiin sekä liuoksen koostumusta ATR FTIR-spektroskopian (Attenuated Total Reflection Fourier Transform Infrared Spectrometer) avulla. Tutkittavina muuttujina olivat mm. sekoitusintensiteetti, sekoitintyyppi, reaktanttien (natriumglutamaatti ja rikkihappo) konsentraatiot sekä syötetyn rikkihapon syöttökohta kiteyttimessä. Työhön sisältyi 36 koetta ja osa kokeista toistettiin tulosten oikeellisuuden tarkistamiseksi. Inline-mittaustulosten verifioimiseksi kidenäytteet analysoitiin myös käyttämällä konfokaali Raman-mikroskooppia. Kidemorfologiaa tutkittiin SEM-kuvien (Scanning Eletronic Microscope) avulla. Työ osoitti, että Raman-spektroskopia on joustava ja luotettava menetelmä saostusprosessin jatkuvaan seurantaan L-glutamiinihapolla. Alhaiset lähtöainepitoisuudet tuottivat pääasiassa ¿¿muotoa, kun taas alhainen sekoitusteho edisti ß-muodon muodostumista. Syöttökohta vaikutti merkittävästi polymorfiaan. Kun rikkihapon syöttökohta oli epäideaalisesti sekoitetulla vyöhykkeellä, nousi ylikylläisyystaso korkeaksi ja päätuote oli tällöin ß-muotoa. 6-lapainen vinolapaturbiini (nousukulma 45o) ja 6-lapainen levyturbiini eivät merkittävästi poikenneet toisistaan muodostuvien polymorfien osalta.

Modeling dynamic behavior in tilting pad gas journal bearings

Thisresearch deals with the dynamic modeling of gas lubricated tilting pad journal bearings provided with spring supported pads, including experimental verification of the computation. On the basis of a mathematical model of a film bearing, a computer program has been developed, which can be used for the simulation of a special type of tilting pad gas journal bearing supported by a rotary spring under different loading conditions time dependently (transient running conditions due to geometry variations in time externally imposed). On the basis of literature, different transformations have been used in the model to achieve simpler calculation. The numerical simulation is used to solve a non-stationary case of a gasfilm. The simulation results were compared with literature results in a stationary case (steady running conditions) and they were found to be equal. In addition to this, comparisons were made with a number of stationary and non-stationary bearing tests, which were performed at Lappeenranta University of Technology using bearings designed with the simulation program. A study was also made using numerical simulation and literature to establish the influence of the different bearing parameters on the stability of the bearing. Comparison work was done with literature on tilting pad gas bearings. This bearing type is rarely used. One literature reference has studied the same bearing type as that used in LUT. A new design of tilting pad gas bearing is introduced. It is based on a stainless steel body and electron beam welding of the bearing parts. It has good operation characteristics and is easier to tune and faster to manufacture than traditional constructions. It is also suitable for large serial production.

Characterization Method for Comminution Behavior of Limestone and Fuel Ash in a Circulating Fluidized Bed Boiler

Työn tavoite oli kehittää karakterisointimenetelmät kalkkikiven ja polttoaineen tuhkan jauhautumisen ennustamiselle kiertoleijukattilan tulipesässä. Kiintoainekäyttäytymisen karakterisoinnilla ja mallintamisella voidaan tarkentaa tulipesän lämmönsiirron ja tuhkajaon ennustamista. Osittain kokeelliset karakterisointimenetelmät perustuvat kalkkikiven jauhautumiseen laboratoriokokoluokan leijutetussa kvartsiputkireaktorissa ja tuhkan jauhatumiseen rotaatiomyllyssä. Karakterisointimenetelmät ottavat huomioon eri-laiset toimintaolosuhteet kaupallisen kokoluokan kiertoleijukattiloissa. Menetelmät kelpoistettiin kaupallisen kokoluokan kiertoleijukattiloista mitattujen ja fraktioittaisella kiintoainemallilla mallinnettujen taseiden avulla. Kelpoistamistaseiden vähäisyydestä huolimatta karakterisointimenetelmät arvioitiin virhetarkastelujen perusteella järkeviksi. Karakterisointimenetelmien kehittämistä ja tarkentamista tullaan jatkamaan.

Customer Expectations and Organizational Buying Behavior in the Flexible Packaging Markets

Tämä työ on tehty yhteistyössä kansainvälisen metsäteollisuusyrityksen Stora Enson kanssa. Työ on osa Stora Enson strategiaa kehitettäessä uusia ja innovatiivisia pakkausmateriaaleja ja ratkaisuja joustopakkausmarkkinoille. Työn päätavoitteina oli selvittää, millaisia odotuksia tuotemerkkienomistajilla ja jatkojalostajilla on joustopakkauksista ja kuinka pakkausten ostopäätökset syntyvät monitahoisessa liikeympäristössä. Työn teoreettinen viitekehys jaettiin kahteen osaan. Asiakasodotuksia lähestyttiin tutkimalla eri palvelu- ja tuotelaadun ulottuvuuksia, ja teollisuuden ostokäyttäytymistä tutkittiin organisaatioiden ostokäyttämistä kuvaavien mallien avulla. Työn empiirisessä osuudessa käytettiin laadullista tutkimusmenetelmää käsittäen asiakashaastatteluja lähinnä Yhdysvalloissa. Haastateltavat yritykset koostuivat maailman johtavista kuluttajatuotteita valmistavista yrityksistä sekä jatkojalostajista. Tutkimustulosten mukaan odotukset pakkauksista liittyvät lähinnä tuotteen suojaamiseen sekä myynnin edistämiseen. Pääodotuksina on myös saada mahdollisimman edullisia papereita, mahdollisimman hyvillä barrier- ja paino-ominaisuuksilla. Tutkimustulokset osoittavat myös, että paperiyhtiöt ovat epäonnistuneet tekemään itseään tunnetuksi teollisuudelle ja heidän odotetaan olevan tulevaisuudessa aggressiivisempia ja innovatiivisempia. Tuotemerkkienomistajat ostavat pakkaukset ja pakkausmateriaalit normaalisti mieluiten jatkojalostajiensa kautta, mutta silti he toivovat yhteistyötä paperintoimittajien kanssa kunhan vain myös jatkojalostajat sisällytetään toimintaan mukaan.

Social Cognition and Behavior in Relationship Context

Social information processing (SIP; Crick & Dodge, 1994) and social-cognitive learning theories have been often used to understand children’s problem behaviors, such as aggression. According to these theories, children’s thinking guides their subsequent behaviors. Although most of us agree that social behavior and underlying thought processes are context-dependent, personality and social development researchers have usually engaged in searching for stable patterns of dispositions and behaviors, ignoring (or treating as error) the variance across different situations and relationship types. This, however, can result in erroneous conclusions and question the interpretation of previous findings. Four studies were conducted to explore the influence of relationship context on children’s social-cognitive evaluations and behavior. Samples were fourth to sixth graders from Estonia and Finland. Social cognitions were assessed by presenting children with hypothetical vignettes where the previously identified relationship partner’s behavior had a negative consequence for the child (Studies I, II, and IV), followed by questions measuring different social-cognitive processes (e.g., hostile attributions, behavioral strategies, outcome expectations and self-efficacy beliefs for aggression). In addition, in Studies II and IV, children provided information about their behavior within a specific relationship context. In Study III, an affective priming paradigm was employed where participants were presented with a short display of photographs of children’s liked and disliked classmates, and unknown peers. The results of this thesis suggest that children’s thinking and behavior are largely influenced by the affective valence of the relationship. Moreover, cognitions guide behavior within the relationship. The current findings offer a fruitful avenue for studying the heterogeneity of peer interactions.

Modelling of North-West Russian market behavior considering technical restrictions of transmission grid

Nowadays the Finnish-Russian electric energy interaction is carried out through the back-to-back DC Vyborg substation and several power plants working synchronously with Finnish power system. Constant amount of energy flows in one direction — from Russia to Finland. But the process of electricity market development in Russian energy system makes the new possibilities of electrical cooperation available. The goal of master's thesis is to analyze the current state and possible evolution trends of North-West Russian system in relation with future possible change in power flow between Russia and Finland. The research is done by modelling the market of North-West Russia and examination of technical grid restrictions. The operational market models of North-West region of Russia for the years 2008 and 2015 were created during the research process. The description of prepared market models together with modelling results and their analysis are shown in the work. The description of power flow study process and results are also presented.

Role and Function of c-Jun Protein Complex in Cancer Cell Behavior

Transcription factors play a crucial role in the regulation of cell behavior by modulating gene expression profiles. Previous studies have described a dual role for the AP-1 family transcription factor c-Jun in the regulation of cellular fate. In various cell types weak and transient activations of c-Jun N-terminal kinase (JNK) and c-Jun appear to contribute to proliferation and survival, whereas strong and prolonged activation of JNK and c-Jun result in apoptosis. These opposite roles played by c-Jun are cell type specific and the molecular mechanisms defining these antonymous c-Jun-mediated responses remain incompletely understood. c-Jun activity in transformed cells is regulated by signalling cascades downstream of oncoproteins such as Ras and Raf. In addition, the pro-proliferative role and the survival promoting function for c-Jun has been described in various cancer models. Furthermore, c-Jun was described to be overexpressed in different cancer types. However, the molecular mechanisms by which c-Jun exerts these oncogenic functions are not all clearly established. Therefore it is of primary interest to further identify molecular mechanisms and functions for c-Jun in cancer. Regulation of gene expression is tightly dependent on accurate protein-protein interactions. Therefore, co-factors for c-Jun may define the functions for c-Jun in cancer. Identification of protein-protein interactions promoting cancer may provide novel possibilities for cancer treatment. In this study, we show that DNA topoisomerase I (TopoI) is a transcriptional co-factor for c-Jun. Moreover, c-Jun and TopoI together promote expression of epidermal growth factor receptor (EGFR) in cancer cells. We also show that the clinically used TopoI inhibitor topotecan reduces EGFR expression. Importantly, the effect of TopoI on EGFR transcription was shown to depend on c-Jun as Jun-/- cells or cells treated with JNK inhibitor SP600125 are resistant to topotecan treatment both in regulation of EGFR expression and cell proliferation. Moreover, c-Jun regulates the nucleolar localization and the function of the ribonucleic acid (RNA) helicase DDX21, a previously identified member of c-Jun protein complex. In addition, c-Jun stimulates rRNA processing by supporting DDX21 rRNA binding. Finally, this study characterizes a DDX21 dependent expression of cyclin dependent kinase (Cdk) 6, a correlation of DDX21 expression with prostate cancer progression and a substrate binding dependency of DDX21 nucleolar localization in prostate cancer cells. Taken together, the results of this study validate the c-Jun-TopoI interaction and precise the c-Jun-DDX21 interaction. Moreover, these results show the importance for protein-protein interaction in the regulation of their cellular functions in cancer cell behavior. Finally, the results presented here disclose new exciting therapeutic opportunities for cancer treatment.

Literature review on permanent magnet generators design and dynamic behavior

This paper is a literature review which describes the construction of state of the art of permanent magnet generators and motors constructing and discusses the current and possible application of these machines in industry. Permanent magnet machines are a well-know class of rotating and linear electric machines used for many years in industrial applications. A particular interest for permanent magnet generators is connected with wind mills, which seem to be becoming increasingly popular nowadays. Geared and direct-driven permanent magnet generators are described. A classification of direct-driven permanent magnet generators is given. Design aspects of permanent magnet generators are presented. Permanent magnet generators for wind turbines designs are highlighted. Dynamics and vibration problems of permanent magnet generators covered in literature are presented. The application of the Finite Element Method for mechanical problems solution in the field of permanent magnet generators is discussed.

Human behavior on the Internet

In this thesis, "Human behavior on the Internet", the human anxiety is conceptualized. The following questions have guided the writing of the thesis: How humans behave with the Internet technology? What goes in their mind? What kinds of behaviors are shown while using the Internet? What is the role of the content on the Internet and especially what are the types of anxiety behavior on the Internet? By conceptualization this thesis aims to provide a model for studying whether humans show signs of less or exacerbated anxiety while using the Internet. The empirical part of this thesis was built on new developed model and user study that utilizes that model. For the user study, the target users were divided into two groups based on their skill level. The user study used both qualitative and quantitative research methods. The qualitative research was conducted using interviews and observational analysis. The quantitative research was conducted in three iterations by using questionnaires and surveys. These results suggest that the significance of human on using technology would be integral part of such a study. The study also suggests that Internet has lulled humans with the sense of dependency to greater extent. In particular, the results identified seven main areas of human anxiety. These forms of anxiety require further studies to encompass human anxiety in more detail.