Behavior of black liquor nitrogen in combustion : formation of cyanate

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

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

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

Keskitehoestimaattorin lisääminen diesel-sähköiseen hybridijärjestelmään

Nykyajan jatkuvasti kiristyvät päästörajoitukset ja ilmastonmuutoksen uhka ovat ajavia voimia kehittämään voimalaitosten tekniikkaa energiatehokkaampaan ja ympäristöystävällisempään suuntaan. Polttomoottoritekniikan parantaminen on tärkeä osa tätä kehitystä, mutta jo nykyisiä moottoreita voitaisiin ajaa energiate-hokkaammin käyttämällä akustoa ja älykästä säätöjärjestelmää apuna. Työssä tutkitaan simulaatioiden avulla voidaanko ulkomerellä toimivan huolto-aluksen energiatehokkuutta parantaa muokkaamalla sen tehon tuottoa keskitehoes-timaattorin ja akuston avulla.

Value based pricing and marketing of marine engines

Objective of the thesis is to create a value based pricing model for marine engines and study the feasibility of implementing such model in the sales organization of a specific segment in the case company’s marine division. Different pricing strategies, concept of “value”, and how perceptions of value can be influenced through value based marketing are presented as theoretical background for the value based pricing model. Forbis and Mehta’s Economic Value to Customer (EVC) was selected as framework to create the value based pricing model for marine engines. The EVC model is based on calculating and comparing life-cycle costs of the reference product and competing products, thus showing the quantifiable value of the company’s own product compared to competition. In the applied part of the thesis, the components of the EVC model are identified for a marine diesel engine, the components are explained, and an example calculation created in Excel is presented. When examining the possibilities to implement in practice a value based pricing strategy based on the EVC model, it was found that the lack of precise information on competing products is the single biggest obstacle to use EVC exactly as presented in the literature. It was also found that sometimes necessary communication channels are missing and that there is simply a lack of interest from some clients and product end-users part to spend time on studying the life-cycle costs of the product. Information on the company’s own products is however sufficient and the sales force is capable to communicate to sufficiently high executive levels in the client organizations. Therefore it is suggested to focus on quantifying and communicating the company’s own value proposition. The dynamic nature of the business environment (variance in applications in which engines are installed, different clients, competition, end-clients etc.) means also that each project should be created its own EVC calculation. This is demanding in terms of resources needed, thus it is suggested to concentrate on selected projects and buyers, and to clients where the necessary communication channels to right levels in the customer organization are available. Finally, it should be highlighted that as literature suggests, implementing a value based pricing strategy is not possible unless the whole business approach is value based.

Implementatiоn оf Sustainability-Оriented Innоvatiоns in Business - Studying Оrganizatiоnal and External Capabilities: Evidence frоm Pоland

The cоncept оf sustainability-оriented innоvatiоn is recent and still under researched. The aim оf the Thesis is tо cоntribute tо the field and investigate hоw dо cоmpanies оperating in Pоland apply sustainability-оriented innоvatiоn (SОI) tо their cоre business activities, what are the differences between variоus business fоrms оf оrganizatiоn in terms оf SОI, and what type оf capabilities facilitate implementatiоn оf SОI. Given early stage оf empirical research оn sustainability-оriented innоvatiоn, an explоratоry-descriptive case study research strategy was taken applying qualitative methоds. 6 interviews with managers and CEОs оf 4 cоmpanies lоcated in Warsaw were cоnducted. In additiоn, twо academic expert panels with specialists frоm University оf Lоdz and Lappeenranta University оf Technоlоgy were carried оut in оrder tо suppоrt the findings. The study fоund оut that in case оf cоmpanies which purpоse is tо create pоsitive impact and develоp sustainable prоducts оr services by using innоvative apprоaches, SОI activities are embedded in оrganizatiоnal culture and prоcess sо that it is difficult tо differentiate between main business activities and SОI. In the оther twо cases SОI practices were in line with cоre business activities thus reflected the main оperatiоns and were determined as a part оf CSR strategy. Activities are industry specific and are cоntingent upоn resоurces and capabilities pоssessed. Amоng list оf success factоrs management suppоrt, CEО’s persоnal values, dedicated and mоtivated team, investments in research and develоpment, оrganizatiоnal culture, nоn-hierarchical cоmmunicatiоns channels, empоwerment оf emplоyees, prоvisiоn оf time and space fоr failures were identified as key оrganizatiоnal capabilities facilitating integratiоn оf SОI practices. Whereas market demand, NGОs’ pressure, regulatiоns enfоrced, access tо external funding, netwоrking and cооperating present external оr cоllabоrative capabilities suppоrting implementatiоn оf sustainability оriented innоvatiоn in cоmpanies. SОI takes a systemic apprоach that drives the transfоrmatiоn tо becоme sustainable business embedding and integrating sоcial, envirоnmental and ecоnоmic value creatiоn tоgether.

The Nature of Object of Perception and Its Role in the Knowledge Concerning the External World

Questions concerning perception are as old as the field of philosophy itself. Using the first-person perspective as a starting point and philosophical documents, the study examines the relationship between knowledge and perception. The problem is that of how one knows what one immediately perceives. The everyday belief that an object of perception is known to be a material object on grounds of perception is demonstrated as unreliable. It is possible that directly perceived sensible particulars are mind-internal images, shapes, sounds, touches, tastes and smells. According to the appearance/reality distinction, the world of perception is the apparent realm, not the real external world. However, the distinction does not necessarily refute the existence of the external world. We have a causal connection with the external world via mind-internal particulars, and therefore we have indirect knowledge about the external world through perceptual experience. The research especially concerns the reasons for George Berkeley’s claim that material things are mind-dependent ideas that really are perceived. The necessity of a perceiver’s own qualities for perceptual experience, such as mind, consciousness, and the brain, supports the causal theory of perception. Finally, it is asked why mind-internal entities are present when perceiving an object. Perception would not directly discern material objects without the presupposition of extra entities located between a perceiver and the external world. Nevertheless, the results show that perception is not sufficient to know what a perceptual object is, and that the existence of appearances is necessary to know that the external world is being perceived. However, the impossibility of matter does not follow from Berkeley’s theory. The main result of the research is that singular knowledge claims about the external world never refer directly and immediately to the objects of the external world. A perceiver’s own qualities affect how perceptual objects appear in a perceptual situation.

Relationship between pulmonary function and indoor air pollution from coal combustion among adult residents in an inner-city area of southwest China

Few studies evaluate the amount of particulate matter less than 2.5 mm in diameter (PM2.5) in relation to a change in lung function among adults in a population. The aim of this study was to assess the association of coal as a domestic energy source to pulmonary function in an adult population in inner-city areas of Zunyi city in China where coal use is common. In a cross-sectional study of 104 households, pulmonary function measurements were assessed and compared in 110 coal users and 121 non-coal users (≥18 years old) who were all nonsmokers. Several sociodemographic factors were assessed by questionnaire, and ventilatory function measurements including forced vital capacity (FVC), forced expiratory volume in 1 s (FEV1), the FEV1/FVC ratio, and peak expiratory flow rate (PEFR) were compared between the 2 groups. The amount of PM2.5 was also measured in all residences. There was a significant increase in the relative concentration of PM2.5 in the indoor kitchens and living rooms of the coal-exposed group compared to the non-coal-exposed group. In multivariate analysis, current exposure to coal smoke was associated with a 31.7% decrease in FVC, a 42.0% decrease in FEV1, a 7.46% decrease in the FEV1/FVC ratio, and a 23.1% decrease in PEFR in adult residents. The slope of lung function decrease for Chinese adults is approximately a 2-L decrease in FVC, a 3-L decrease in FEV1, and an 8 L/s decrease in PEFR per count per minute of PM2.5 exposure. These results demonstrate the harmful effects of indoor air pollution from coal smoke on the lung function of adult residents and emphasize the need for public health efforts to decrease exposure to coal smoke.

Development and chemical characterization of flour obtained from the external mesocarp of "pequizeiro" fruit

The objective of this work was to develop a recommendation for the chemical peeling of pequi fruit and characterize the flour obtained from the external mesocarp of "Pequizeiro", pequi tree (Caryocar brasiliense Camb.). The technology applied to obtain the external mesocarp pequi flour included the epicarp removal with NaOH solution. The Response Surface Method was used to optimize the chemical peeling process by applying the Central Composite Rotatable Design, with eleven trials including three replicates at the central point, varying the NaOH aqueous solution concentration and fruit immersion time. The mass loss was evaluated through the analysis of variance and using bi and three dimensional graphs. The chemical characteristics of the external mesocarp pequi flour evaluated were: moisture content, ashes, proteins, lipids, total carbohydrates, dietary fiber, and some minerals. The best combination for an efficient removal of the fruit peel with the lowest mass loss was reached with 7.05 minutes of immersion in a 5.08 g.L-1 NaOH aqueous solution. This study indicated that the external mesocarp pequi flour is a food source rich in dietary fiber, carbohydrates, ashes, magnesium, calcium, manganese, and copper, but it is poor in lipids, zinc, and iron.

Evaluation of hygienic-sanitary conditions of hospital nutrition and dietary services from the perspectives of internal and external auditors

The objective of this study was to evaluate the hygienic-sanitary conditions of hospital nutrition and dietary services using external and internal auditors. Eleven hospitals were evaluated for their nutrition and dietary services using an evaluation checklist based on food safety requirements in the current legislation. The checklist was applied by an internal auditor (a technical supervisor) and an external auditor (a professional with experience in food services) between August and October 2011. According to the number of items on the evaluation checklist that were considered adequate, the hospital facilities were ranked as excellent, good, regular, bad, or very bad. The results obtained by the auditors were compared. According to these results, it can be said that most of the hospital nutrition and dietary services were rated as good for overall quality by the internal auditor, while the external auditor classified them as Regular. There was a clear difference between the evaluations of the auditors, both in terms of the number of items considered adequate and the overall requirements' average score. It can be concluded that hospital nutrition and dietary services should meet safety requirements in order to provide food. These facilities should have external audits conducted as a way to prevent routine problems from being perpetuated.

External debt in developing economies: assessment and policy issues

More than one decade after the external debt restructuring (the Brady Plan), a great amount of literature has been published concerning the balance sheet factors in developing countries. The staff of international multilateral institutions joined with reputable academics in this great controversy. The external debt problem of the developing countries is back and once more reflections on its cause and on policy recommendations are analytically distinct. Our main task is to reflect on the recent external debt dynamics and assess how this debt has evolved. Our findings indicate that the susceptibility of some developing countries to default is associated with global imbalance, that is, the way they borrow.

From the 'Miracle' to the 'Lost Decade': intersectoral transfers and external credit in the Brazilian economy

The present paper examines the Brazilian experience from the 'Economic Miracle' to the 'Lost Decade'. Its aim is to advance an alternative measurement of the flows of extraordinary wealth (i.e. ground-rent and net external credit) available for appropriation in the Brazilian economy and to asses their relevance in sustaining the process of accumulation of industrial capital. That is done in order to provide further and more accurate evidence to the claim that the evolution of the Brazilian process of capital accumulation has been extremely dependent on the evolution of those masses of extraordinary wealth.

Preparation and Investigation of Bio-coal Mixture Fuels Used in Large Diesel Engines

Coal slurry was of vital interest during the last century due to its potential as an alternative fuel where liquid fuels were necessary. Recently, environmental impacts of the traditional fuels, similarities of bio-coal to that of coal, and huge bio-coal supply has attracted the attention to prepare bio-coal slurries as a new fuel. Rudolf Diesel who invented the diesel engine on 1895 was of the opinion that diesel engines are capable to use different kinds of fuels due to the special design. He tried some kind of vegetable oil to operate on his IC engine. Recently, due to high energy density and more environmentally friendly fuel, researchers believe that bio-coal slurries could act as a new alternative fuel in large diesel engines. Loads of research on different kinds of bio-coal slurry were done by the other researchers worldwide and a lot of progress to boost slurry’s quality were achieved recently. The present study aims to achieve the ideal condition of different factors affecting on the quality of bio-coal slurry. One charcoal sample and two kinds of torrefied wood were used to investigate and compare the reaction of various factors. The results show a great gap between the quality of slurries made of different samples and more researches are necessary to fully understand the impact of the different parameter and improving the quality.

EXPLOITING SCENARIO PLANNING FOR STRATEGIC ASSESSMENT OF THE EXTERNAL BUSINESS ENVIRONMENT Future insights of the European pet food sector

The purpose of this study is to explore how scenarios can be exploited in strategic assessment of the external business environment. One of the key challenges for managers worldwide is to adapt their businesses to the ever-changing business environment. As the companies’ external business environment is constantly presenting new opportunities and threats, it is extremely important that companies continuously monitor the possible changes happening around it. As the speed of change rises, assessing the future has become more and more vital. The study was conducted as an exploratory research and the research strategy was influenced by scenario planning and case study strategy. The study examined the European pet food sector from the future point of view. Qualitative study was chosen as research approach and empirical data was collected primarily by seven expert interviews. The secondary data about the sector was applied as complementary empirical data. In the theoretical part of the research it was discovered that nowadays, traditional analysis frameworks are ill-suited for strategic assessment of the external business environment. This is why a self-created combination framework for analysis was employed both as study’s theoretical framework and analysis technique. Furthermore, the framework formed the base for interview questions. Both in theoretical and the empirical part of the study it was found that today, in strategic assessment of the external business environment, besides setting focus on the current situation, it is important to concentrate also on the future. The traditional analysis frameworks offer a good starting point for collecting relevant data but they do not encourage conducting a deeper analysis. By adding characteristics from scenario planning to these more traditional tools, a new analysis framework was created, which ensured the more comprehensive analysis. By understanding the interconnections between discovered phenomena and changes, and by recognizing uncertainties, the user is helped to reflect the environment more profoundly. The contributions of the study are both theoretical and managerial. A new analysis framework strives to answer to the current needs for strategic assessment of external business environment and the framework was tested in the context of European pet food sector. When it comes to managerial contributions, the importance lies in understanding the future. Managers must take future into account and understand that future includes various possibilities which all must be reflected

Distribution of Smart Solutions for External Lighting in Switzerland - Case C2 Smartlight Ltd.

Establishing of export operations is the key to the competitiveness for all producing companies in high-tech industry. Distribution partnerships between exporting producer and local distributors of relevant foreign market are utilized by SMEs to gain cost-efficiency of operation. The purpose of this study was to investigate the Swiss market of outdoor lighting solutions and propose distribution channels for the case of company C2 SmartLight Ltd. The literature framework consists of three main parts: description of distribution channels for business products, the selection process of the distributor and management of the distributors. The empirical part of this study composed of the observation of Swiss lighting market, highlighting key customers, trends of energy efficiency and key industry players of the lighting market. The aim was to identify potential distribution channels, which reach the target customer groups and identify the market opportunity. Secondly, the data was collected through semi-structured phone interviews. The company, which operates in outdoor lighting business and has an established distributor in Switzerland, was interviewed and used as a benchmark. As a result of this research the market opportunity for distribution of C2 SmartLight products was identified based on potential customers and market need. C2 SmartLight Ltd. should establish a connection with wholesalers that distribute easy to handle and store electrical equipment. The results of this study can be used by other SME companies, operating in a similar field of economy, for selection of distributors.