Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

Distribution and role of macrophytes in coastal lagoons : implications of critical shifts

Crossroads, crucibles and refuges are three words that may describe natural coastal lagoon environments. The words refer to the complex mix of marine and terrestrial influences, prolonged dilution due to the semi-enclosed nature and the function of a habitat for highly diverse plant and animal communities, some of which are endangered. To attain a realistic picture of the present situation, high vulnerability to anthropogenic impact should be added to the description. As the sea floor in coastal lagoons is usually entirely photic, macrophyte primary production is accentuated compared with open sea environments. There is, however, a lack of proper knowledge on the importance of vegetation for the general functioning of coastal lagoon ecosystems. The aim of this thesis is to assess the role of macrophyte diversity, cover and species identity over temporal and spatial scales for lagoon functions, and to determine which steering factors primarily restrict the qualitative and quantitative composition of vegetation in coastal lagoons. The results are linked to patterns of related trophic levels and the indicative potential of vegetation for assessment of general conditions in coastal lagoons is evaluated. This thesis includes five field studies conducted in flads and glo-flads in the brackish water northern Baltic Sea. Flads and glo-flads are defined as a Baltic variety of coastal lagoons, which due to an inlet threshold and post-glacial landuplift slowly will be isolated from the open sea. This process shrinks inlet size, increases exposure and water retention, and is called habitat isolation. The studied coastal lagoons are situated in the archipelago areas of the eastern coast of Sweden, the Åland Islands and the south-west mainland of Finland, where land-uplift amounts to ca. 5 mm/ per year. Out of 400 evaluated sites, a total of 70 lagoons varying in inlet size, archipelago position and anthropogenic influence to cover for essential environmental variation were chosen for further inventory. Vegetation composition, cover and richness were measured together with several hydrographic and morphometric variables in the lagoons both seasonally and inter-annually to cover for general regional, local and temporal patterns influencing lagoon and vegetation development. On smaller species-level scale, the effects of macrophyte species identity and richness for the fish habitat function were studied by examining the influence of plant interaction on juvenile fish diversity. Thus, the active election of plant monoand polycultures by fish and the diversity of fish in the respective culture were examined and related to plant height and water depth. The lagoons and vegetation composition were found to experience a regime shift initiated by increased habitat isolation along with land-uplift. Vegetation composition altered, richness decreased and cover increased forming a less isolated and more isolated regime, named the vascular plant regime and charophyte regime, respectively according to the dominant vegetation. As total phosphorus in the water, turbidity and the impact of regional influences decreased in parallel, the dominance of charophytes and increasing cover seemed to buffer and stabilize conditions in the charophyte regime and indicated an increased functional role of vegetation for the lagoon ecosystem. The regime pattern was unaffected by geographical differences, while strong anthropogenic impact seemed to distort the pattern due to loss of especially Chara tomentosa L. in the charophyte regime. The regimes were further found unperturbed by short-time temporal fluctuations. In fact the seasonal and inter-annual dynamics reinforced the functional difference between the regimes by the increasing role of vegetation along habitat isolation and the resemblance to lake environments for the charophyte regime. For instance, greater total phosphorus and chlorophyll a concentrations in the water in the beginning of the season in the charophyte regime compared with the vascular plant regime presented a steeper reduction to even lower values than in the vascular plant regime along the season. Despite a regional importance and positive relationship of macrophyte diversity in relation to trophic diversity, species identity was underlined in the results of this thesis, especially with decreasing spatial scale. This result was supported partly by the increased role of charophytes in the functioning of the charophyte regime, but even more explicitly by the species-specific preference of juvenile fish for tall macrophyte monocultures. On a smaller species-level scale, tall plant species in monoculture seemed to be able to increase their length, indicating that negative selection forms preferred habitat structures, which increase fish diversity. This negative relationship between plant and fish diversity suggest a shift in diversity patterns among trohic levels on smaller scale. Thus, as diversity patterns seem complex and diverge among spatial scales, it might be ambiguous to extend the understanding of diversity relationships from one trophic level to the other. All together, the regime shift described here presents similarities to the regime development in marine lagoon environments and shallow lakes subjected to nutrient enrichment. However, due to nutrient buffering by vegetation with increased isolation and water retention as a consequence of the inlet threshold, the development seems opposite to the course along an eutrophication gradient described in marine lagoons lacking an inlet threshold, where the role of vegetation decreases. Thus, the results imply devastating consequences of inlet dredging (decreasing isolation) in terms of vegetation loss and nutrient release, and call for increased conservational supervision. Especially the red listed charophytes would suffer negatively from such interference and the consequences are likely to also deteriorate juvenile fish production. The fact that a new species to Finland, Chara connivens Salzm. Ex. Braun 1835 was discovered during this study further indicates a potential of the lagoons serving as refuges for rare species.

Biomass fractionation

The objective of this master's thesis was to develop a process to increase the value of residual fungal biomass as an animal feed. The increase in value is achieved by enriching the protein content in the biomass and potentially isolating other valuable fractions for productisation. In the literature part of this thesis the composition of fungal biomass and fungal cell wall and the factors affecting them during cultivation are presented. The possible processing options are also presented and evaluated. The soy protein and single cell protein product manufacturing processes are used as examples due to the lack of fungal biomass fractionation processes found in published literature. The second part of this thesis was performed by making laboratory experiments on the developed process, which consisted of acid hydrolysis with subsequent ethanol extraction. Chitin was precipitated from the acid hydrolysate filtrate. The experiments were conducted with three different hydrolysis temperatures and three different acid concentrations. The optimal hydrolysis conditions were 60 °C with 10 %-vol acid concentration. Optimal conditions in hydrolysis resulted in 30 % increase in protein content in the final biomass. The conceptual process was modelled to scale of 10 000 t/a biomass feed. The mass and energy balances were based on the laboratory experiments. Economic calculations were performed to determine the maximal capital expense while achieving 10 % internal rate of return for the investment. For the basic case the capital expense threshold was 25.8 M€. Four optional cases and parameter sensitivity analysis were performed to determine the effects of changes in the process. The chitin sales had the greatest impact of the individual parameters.

Maanpuolustustahto asevelvollisen koulutuksen ja palveluksen onnistumista selittävänä tekijänä

Lähtökohta tälle tutkimukselle oli havainto siitä, että varusmiehillä maanpuolustustahto ja taisteluluottamus korreloivat. Tämä huomio oli mahdollista tehdä aikaisemmissa varusmiesaineistoilla tehdyissä tutkimuksissa, joissa olin ollut mukana. Tutkimuksen aineistoina olivat useat puolustusvoimissa kerätyt varusmiesten kyselytutkimusaineistot. Vertailuaineistoina käytin reserviläisille kertausharjoituksissa tehtyjen kyselyiden aineistoja. Olennaista oli selvittää, säilyikö havaittu riippuvuus kun muita mahdollisia tekijöitä otettiin huomioon. Tutkimus oli aikaisemmin kerättyjen aineistojen sekundaarianalyysi ja tutkijana en ollut voinut vaikuttaa kyselyjen sisältöön tai käytettyjen muuttujien ja mittareiden valintaan. Aineistot on kerätty kuvaileviin tarkoituksiin ja tästä syystä tämä tutkimus oli tilastollisesti kuvaileva. Keskeiset käytetyt aineistot olivat varusmiesten kotiuttamiskyselyiden eli loppukyselyiden aineistot kaikista varuskunnista vuosilta 2000 – 2008 sekä vuonna 2010 Siilasmaan työryhmää varten kerätty aineisto kolmesta varuskunnasta. Vuoden 2010 varusmiestutkimus oli toteutettu siten, että kysely tehtiin sekä palveluksen alussa että lopussa. Tässä aineistossa käytettiin monipuolisesti varusmiesten psykososiaalisen toimintakyvyn erilaisia mittareita. Maanpuolustustahto on käsitteellisesti laaja kokonaisuus, kuitenkin tässä tutkimuksessa se oli operationalisoitava käytettävissä olleiden osioiden avulla. Maanpuolustustahtoa tarkasteltiin sekä henkilökohtaisena että yleisenä maanpuolustustahtona sekä niiden yhdistelmänä, josta käytettiin myös nimitystä maanpuolustusajattelu. Käsitteellisesti suppeampi taisteluluottamus operationalisoitiin siten, että muuttujana se kuvasi varusmiehen luottamusta aseisiinsa, saamaansa koulutukseen sekä lähiryhmäänsä. Taisteluluottamuksen mittaamisen taustalla oli ajatus siitä, että tämän yksilökohtaisen mittarin keskiarvo on joukon koulutuksen onnistuneisuuden estimaatti. Taisteluluottamus oli tutkimuksessa varsinainen tulosmuuttuja. Tulosten perusteella yksittäisten varusmiesten psykososiaalisessa toimintakyvyssä on eroja. Erityisesti erottui yksittäisenä tekijänä sosiaalisuus, joka summamuuttujana oli muodostettu varusmiestutkimus 2010:n aineistossa Maanpuolustuskorkeakoulun Käyttäytymistieteen laitoksen laatimista osioista. Sosiaalisuus ennusti voimakkaasti varusmiehen etenemistä koulutuksessa aina johtajakoulutukseen saakka. Sosiaalisuuden kontrollointi tilastollisesti ei poistanut maanpuolustusajattelun ja taisteluluottamuksen välistä riippuvuutta. Varusmiestutkimus 2010 aineistossa oli mahdollista tarkastella maanpuolustusajattelun muutosta palvelusaikana ja muutoksen yhteyttä psykososiaalisen toimintakyvyn kuvaajiin. Stressaantumistaipumus ja neuroottisuus olivat yhteydessä maanpuolustustahdon laskuun. Tunteiden hallinnan kyky tuki varusmiehen maanpuolustustahdon ja taisteluluottamuksen kehittymistä. Tilastollinen kuvaus toteutettiin Mplus-ohjelmistolla lasketulla rakenneyhtälömallilla. Aineistoon sopiva malli oli mahdollista löytää. Mallin mukaan sosiaalinen pääoman yksilökohtaisena resurssina antaa mahdollisuuden kehittää ja säilyttää maanpuolustusajattelua, joka on yhteydessä itseluottamuksen luontoiseen taisteluluottamukseen varusmieskoulutuksen päättyessä. Koulutuksen aikana joukkoon kehittynyt kiinteys ja luottamus tukevat tätä kehitystä. Joukkotuotantomallilla saadaan aikaan joukkoja, joissa taisteluluottamus on yleensä tarvittavalla tasolla ja niitä voidaan käyttää osoitettuihin tehtäviin. Kertausharjoitukset ylläpitävät kiinteyttä, taisteluluottamusta ja sitä kautta joukon suorituskykyä. Tutkimuksessa havaittiin myös, että pysyvissä miehistön ryhmissä, joissa ryhmänjohtaja ja/tai jäseniä ei vaihtunut, koulutuksen tulokset olivat parempia kuin muuttuneissa ryhmissä. Edelleen havaittiin, että 12 kuukautta palvelleiden miehistön jäsenten joukossa palvelusmotivaatio laski enemmän kuin muissa varusmiesryhmissä. Yhdestätoista koulutuksen ja tutkimuksen asiantuntijasta koottu ryhmä arvioi tutkimuksen tuloksia sovelletulla Q-menetelmällä Facilitate Pro -ohjelmistoa käyttäen. Menettely tuotti lisänäkökohtia tulosten arviointiin sekä niiden soveltamiseen.

Uuden muoviteollisuustuotteen kehittäminen analyyttista hierarkiaprosessia hyödyntäen

Tämä diplomityö on tehty case yritykselle nimeltä yritys X. Yritys X valmistaa alueelliseen lämmön- ja käyttöveden jakamiseen tarkoitettuja eristettyjä muoviputkia. Viime vuosina yrityksen kilpailijat ovat onnistuneet kehittämään omien vastaavien tuotteidensa ominaisuuksia, minkä seurauksena yritys X:n asema markkinoilla on heikentynyt. Vastauksena kiristyneeseen markkinatilanteeseen yritys X on kehittänyt kolme uutta potentiaalista tuotekonseptia, joista yhtä suunnitellaan kehitettäväksi nykyisen tuotteen rinnalle. Uusien tuotekonseptien keskinäinen vertailu on kuitenkin osoittautunut haasteelliseksi. Tämän työn päätavoitteena on hyödyntää analyyttista hierarkiaprosessia ja antaa sen perusteella suositus parhaan tuotekonseptin valinnasta. Työ sisältää kirjallisen osion, jossa käydään läpi tuotekehitystoimintaa yleisesti sekä esitellään analyyttisen hierarkiaprosessin hyödyntäminen yksityiskohtaisesti. Työn jälkimmäisessä osiossa paneudutaan tarkemmin käytännön ongelmaan ja esitellään kuinka analyyttista hierarkiaprosessia on hyödynnetty yritys X:n tapauksessa. Keskeisinä tuloksina työn lopussa esitellään analyyttisen hierarkiaprosessin avulla määritetyt päätöskriteerien painoarvot, vaihtoehtojen saamat kokonaispainoarvot sekä annetaan suositus uuden tuotekonseptin valinnasta.

Mallinnusinformaation hyödyntäminen ohjelmistokehityksessä

Ohjelmistoprosesseissa kulkee käytännössä sama tieto muuntuen eri vaiheissa käyttökohteensa mukaan. Tätä mallinnusinformaatiota on mahdollista siirtää ja käyttää uudelleen, mikä säästää resursseja ja vähentää riskejä kaikissa projektin vaiheissa. Projektin alussa ohjelmiston toimintoja suunnitellaan ja niitä mallinnetaan esim. UML-malleilla. Tätä mallinnusinformaatiota hallitaan erilaisilla CASE-työkaluilla, joiden avullamalleja on helppo konvertoida toteutusvaihetta varten lähdekoodiksi. Lähdekoodivoidaan tuoda takaisin malliksi jatkosuunnittelua varten, jos työkalu tukee ominaisuutta. Testausvaiheessa lähdekoodi voidaan parsia, jotta siitä saadaan esille olennainen mallinnusinformaatio testejä varten. Lopulta dokumentaatiota voidaan generoida automaattisesti esim. Javadocilla. Mallinnusinformaation hyödyntäminen onnistuu hyvin teoriassa, mutta se ei ole niin suoraviivaista käytännössä. Tämänhetkiset työkalut eivät ole tarpeeksi joustavia mallinnusinformaation palauttamiseksi edellisiin vaiheisiin, joten ne ajavat toteuttamaan projekteja lineaarisesti. Keskikokoisessakin ohjelmistoprojektissa on suuri määrä mallinnusinformaatiota ja se lisää haasteita. Vaikka työkalut ovat kankeita, mallinnusinformaation hyödyntämisen on koettu tehostavan ohjelmistoprosesseja. Siksi sen keinoja tutkitaan ahkerasti.

Innovation Process Management and System Modelling

Työn tavoitteena oli perehtyä innovaatiojohtamisen ja järjestelmän soveltamiseen prosessiteollisuuden toimintaympäristöön. Kirjallisuuslähteitä apuna käyttäen perehdyttiin liiketoimintaympäristön innovaatiojohtamiselle asettamiin vaatimuksiin ja erilaisiin innovaatiojärjestelmiin. Olennaisena osana innovaatiojohtamiseen liittyy sidosryhmien tarpeiden ja niiden tarjoamien resurssien huomioiminen toiminnassa. Myöskin tuotekehityksen menetelmät ja työkalut ovat omalta osaltaan merkittävässä asemassa toiminnan tehokkuutta arvioitaessa. Innovaatiojärjestelmä tulee sopeuttaa yrityksen toimintoihin ja sen erityispiirteet huomioonottaen siten, että toiminnan johtaminen prosessina tuo yritykselle ja sen sidosryhmille lisäarvoa. Innovaatiojärjestelmän luominen yritykselle on ainayksilöllinen prosessi ja siihen ei ole olemassa yleispätevää menetelmää, joka voitaisiin ottaa käyttöön sellaisenaan. Yritys, jonka liiketoiminta keskittyy kuitupohjaisten pakkausmateriaalien valmistamiseen, joutuu täyttämään toiminnassaan materiaalintoimittajien, omien tuotantoprosessiensa ja asiakkaiden sekä jopa loppukäyttäjien uusille tuotteille luomat odotukset. Innovaatiojohtamista sävyttää toiminnan tulosten suuri epävarmuus ja sen vaativien aineellisten ja henkisten resurssien mittavuus. Innovaatiotoiminnan johtaminen prosessina, käyttäen hyväksi järjestelmämallia, tavoittelee systemaattista ja asetettujen kriteerien täyttämää lähestymistapaa tuotekehityksen ja uusien liiketoimintainnovaatioiden alueella. Kehitetyn mallin tulee palvella monimutkaista liiketoimintaympäristöä, jokatoisaalta perustuu tehokkaaseen massatuotantoon ja toisaalta pyrkii erilaistumaan palvelemalla sekä huomioimalla asiakkaidensa tuotteille asettamat vaatimukset.

Effect of hydrodynamics on modelling, monitoring and control of crystallization

Crystallization is a purification method used to obtain crystalline product of a certain crystal size. It is one of the oldest industrial unit processes and commonly used in modern industry due to its good purification capability from rather impure solutions with reasonably low energy consumption. However, the process is extremely challenging to model and control because it involves inhomogeneous mixing and many simultaneous phenomena such as nucleation, crystal growth and agglomeration. All these phenomena are dependent on supersaturation, i.e. the difference between actual liquid phase concentration and solubility. Homogeneous mass and heat transfer in the crystallizer would greatly simplify modelling and control of crystallization processes, such conditions are, however, not the reality, especially in industrial scale processes. Consequently, the hydrodynamics of crystallizers, i.e. the combination of mixing, feed and product removal flows, and recycling of the suspension, needs to be thoroughly investigated. Understanding of hydrodynamics is important in crystallization, especially inlargerscale equipment where uniform flow conditions are difficult to attain. It is also important to understand different size scales of mixing; micro-, meso- and macromixing. Fast processes, like nucleation and chemical reactions, are typically highly dependent on micro- and mesomixing but macromixing, which equalizes the concentrations of all the species within the entire crystallizer, cannot be disregarded. This study investigates the influence of hydrodynamics on crystallization processes. Modelling of crystallizers with the mixed suspension mixed product removal (MSMPR) theory (ideal mixing), computational fluid dynamics (CFD), and a compartmental multiblock model is compared. The importance of proper verification of CFD and multiblock models is demonstrated. In addition, the influence of different hydrodynamic conditions on reactive crystallization process control is studied. Finally, the effect of extreme local supersaturation is studied using power ultrasound to initiate nucleation. The present work shows that mixing and chemical feeding conditions clearly affect induction time and cluster formation, nucleation, growth kinetics, and agglomeration. Consequently, the properties of crystalline end products, e.g. crystal size and crystal habit, can be influenced by management of mixing and feeding conditions. Impurities may have varying impacts on crystallization processes. As an example, manganese ions were shown to replace magnesium ions in the crystal lattice of magnesium sulphate heptahydrate, increasing the crystal growth rate significantly, whereas sodium ions showed no interaction at all. Modelling of continuous crystallization based on MSMPR theory showed that the model is feasible in a small laboratoryscale crystallizer, whereas in larger pilot- and industrial-scale crystallizers hydrodynamic effects should be taken into account. For that reason, CFD and multiblock modelling are shown to be effective tools for modelling crystallization with inhomogeneous mixing. The present work shows also that selection of the measurement point, or points in the case of multiprobe systems, is crucial when process analytical technology (PAT) is used to control larger scale crystallization. The thesis concludes by describing how control of local supersaturation by highly localized ultrasound was successfully applied to induce nucleation and to control polymorphism in reactive crystallization of L-glutamic acid.

A study of combustion phenomena in circulating fluidized beds by developing and applying experimental and modelling methods for laboratory-scale reactors

The results shown in this thesis are based on selected publications of the 2000s decade. The work was carried out in several national and EC funded public research projects and in close cooperation with industrial partners. The main objective of the thesis was to study and quantify the most important phenomena of circulating fluidized bed combustors by developing and applying proper experimental and modelling methods using laboratory scale equipments. An understanding of the phenomena plays an essential role in the development of combustion and emission performance, and the availability and controls of CFB boilers. Experimental procedures to study fuel combustion behaviour under CFB conditions are presented in the thesis. Steady state and dynamic measurements under well controlled conditions were carried out to produce the data needed for the development of high efficiency, utility scale CFB technology. The importance of combustion control and furnace dynamics is emphasized when CFB boilers are scaled up with a once through steam cycle. Qualitative information on fuel combustion characteristics was obtained directly by comparing flue gas oxygen responses during the impulse change experiments with fuel feed. A one-dimensional, time dependent model was developed to analyse the measurement data Emission formation was studied combined with fuel combustion behaviour. Correlations were developed for NO, N2O, CO and char loading, as a function of temperature and oxygen concentration in the bed area. An online method to characterize char loading under CFB conditions was developed and validated with the pilot scale CFB tests. Finally, a new method to control air and fuel feeds in CFB combustion was introduced. The method is based on models and an analysis of the fluctuation of the flue gas oxygen concentration. The effect of high oxygen concentrations on fuel combustion behaviour was also studied to evaluate the potential of CFB boilers to apply oxygenfiring technology to CCS. In future studies, it will be necessary to go through the whole scale up chain from laboratory phenomena devices through pilot scale test rigs to large scale, commercial boilers in order to validate the applicability and scalability of the, results. This thesis shows the chain between the laboratory scale phenomena test rig (bench scale) and the CFB process test rig (pilot). CFB technology has been scaled up successfully from an industrial scale to a utility scale during the last decade. The work shown in the thesis, for its part, has supported the development by producing new detailed information on combustion under CFB conditions.

Generalized Differential Evolution for Global Multi-Objective Optimization with Constraints

The objective of this thesis work is to develop and study the Differential Evolution Algorithm for multi-objective optimization with constraints. Differential Evolution is an evolutionary algorithm that has gained in popularity because of its simplicity and good observed performance. Multi-objective evolutionary algorithms have become popular since they are able to produce a set of compromise solutions during the search process to approximate the Pareto-optimal front. The starting point for this thesis was an idea how Differential Evolution, with simple changes, could be extended for optimization with multiple constraints and objectives. This approach is implemented, experimentally studied, and further developed in the work. Development and study concentrates on the multi-objective optimization aspect. The main outcomes of the work are versions of a method called Generalized Differential Evolution. The versions aim to improve the performance of the method in multi-objective optimization. A diversity preservation technique that is effective and efficient compared to previous diversity preservation techniques is developed. The thesis also studies the influence of control parameters of Differential Evolution in multi-objective optimization. Proposals for initial control parameter value selection are given. Overall, the work contributes to the diversity preservation of solutions in multi-objective optimization.

Fraud detection in the banking sector : a multi-agent approach

Fraud is an increasing phenomenon as shown in many surveys carried out by leading international consulting companies in the last years. Despite the evolution of electronic payments and hacking techniques there is still a strong human component in fraud schemes. Conflict of interest in particular is the main contributing factor to the success of internal fraud. In such cases anomaly detection tools are not always the best instruments, since the fraud schemes are based on faking documents in a context dominated by lack of controls, and the perpetrators are those ones who should control possible irregularities. In the banking sector audit team experts can count only on their experience, whistle blowing and the reports sent by their inspectors. The Fraud Interactive Decision Expert System (FIDES), which is the core of this research, is a multi-agent system built to support auditors in evaluating suspicious behaviours and to speed up the evaluation process in order to detect or prevent fraud schemes. The system combines Think-map, Delphi method and Attack trees and it has been built around audit team experts and their needs. The output of FIDES is an attack tree, a tree-based diagram to ”systematically categorize the different ways in which a system can be attacked”. Once the attack tree is built, auditors can choose the path they perceive as more suitable and decide whether or not to start the investigation. The system is meant for use in the future to retrieve old cases in order to match them with new ones and find similarities. The retrieving features of the system will be useful to simplify the risk management phase, since similar countermeasures adopted for past cases might be useful for present ones. Even though FIDES has been built with the banking sector in mind, it can be applied in all those organisations, like insurance companies or public organizations, where anti-fraud activity is based on a central anti-fraud unit and a reporting system.

Chromatographic recovery of chemicals from acidic biomass hydrolysates

Lignocellulosic biomasses (e.g., wood and straws) are a potential renewable source for the production of a wide variety of chemicals that could be used to replace those currently produced by petrochemical industry. This would lead to lower greenhouse gas emissions and waste amounts, and to economical savings. There are many possible pathways available for the manufacturing of chemicals from lignocellulosic biomasses. One option is to hydrolyze the cellulose and hemicelluloses of these biomasses into monosaccharides using concentrated sulfuric acid as catalyst. This process is an efficient method for producing monosaccharides which are valuable platforn chemicals. Also other valuable products are formed in the hydrolysis. Unfortunately, the concentrated acid hydrolysis has been deemed unfeasible mainly due to high chemical consumption resulting from the need to remove sulfuric acid from the obtained hydrolysates prior to the downstream processing of the monosaccharides. Traditionally, this has been done by neutralization with lime. This, however, results in high chemical consumption. In addition, the by-products formed in the hydrolysis are not removed and may, thus, hinder the monosaccharide processing. In order to improve the feasibility of the concentrated acid hydrolysis, the chemical consumption should be decreased by recycling of sulfuric acid without neutralization. Furthermore, the monosaccharides and the other products formed in the hydrolysis should be recovered selectively for efficient downstream processing. The selective recovery of the hydrolysis by-products would have additional economical benefits on the process due to their high value. In this work, the use of chromatographic fractionation for the recycling of sulfuric acid and the selective recovery of the main components from the hydrolysates formed in the concentrated acid hydrolysis was investigated. Chromatographic fractionation based on the electrolyte exclusion with gel type strong acid cation exchange resins in acid (H+) form as a stationary phase was studied. A systematic experimental and model-based study regarding the separation task at hand was conducted. The phenomena affecting the separation were determined and their effects elucidated. Mathematical models that take accurately into account these phenomena were derived and used in the simulation of the fractionation process. The main components of the concentrated acid hydrolysates (sulfuric acid, monosaccharides, and acetic acid) were included into this model. Performance of the fractionation process was investigated experimentally and by simulations. Use of different process options was also studied. Sulfuric acid was found to have a significant co-operative effect on the sorption of the other components. This brings about interesting and beneficial effects in the column operations. It is especially beneficial for the separation of sulfuric acid and the monosaccharides. Two different approaches for the modelling of the sorption equilibria were investigated in this work: a simple empirical approach and a thermodynamically consistent approach (the Adsorbed Solution theory). Accurate modelling of the phenomena observed in this work was found to be possible using the simple empirical models. The use of the Adsorbed Solution theory is complicated by the nature of the theory and the complexity of the studied system. In addition to the sorption models, a dynamic column model that takes into account the volume changes of the gel type resins as changing resin bed porosity was also derived. Using the chromatography, all the main components of the hydrolysates can be recovered selectively, and the sulfuric acid consumption of the hydrolysis process can be lowered considerably. Investigation of the performance of the chromatographic fractionation showed that the highest separation efficiency in this separation task is obtained with a gel type resin with a high crosslinking degree (8 wt. %); especially when the hydrolysates contain high amounts of acetic acid. In addition, the concentrated acid hydrolysis should be done with as low sulfuric acid concentration as possible to obtain good separation performance. The column loading and flow rate also have large effects on the performance. In this work, it was demonstrated that when recycling of the fractions obtained in the chromatographic fractionation are recycled to preceding unit operations these unit operations should included in the performance evaluation of the fractionation. When this was done, the separation performance and the feasibility of the concentrated acid hydrolysis process were found to improve considerably. Use of multi-column chromatographic fractionation processes, the Japan Organo process and the Multi-Column Recycling Chromatography process, was also investigated. In the studied case, neither of these processes could compete with the single-column batch process in the productivity. However, due to internal recycling steps, the Multi-Column Recycling Chromatography was found to be superior to the batch process when the product yield and the eluent consumption were taken into account.

Additional revenue opportunities in pulp mills and their impacts on the kraft process

Although the concept of multi-products biorefinery provides an opportunity to meet the future demands for biofuels, biomaterials or chemicals, it is not assured that its implementation would improve the profitability of kraft pulp mills. The attractiveness will depend on several factors such as mill age and location, government incentives, economy of scale, end user requirements, and how much value can be added to the new products. In addition, the effective integration of alternative technologies is not straightforward and has to be carefully studied. In this work, detailed balances were performed to evaluate possible impacts that lignin removal, hemicelluloses recovery prior to pulping, torrefaction and pyrolysis of wood residues cause on the conventional mill operation. The development of mill balances was based on theoretical fundamentals, practical experience, literature review, personal communication with technology suppliers and analysis of mill process data. Hemicelluloses recovery through pre-hydrolysis of chips leads to impacts in several stages of the kraft process. Effects can be observed on the pulping process, wood consumption, black liquor properties and, inevitably, on the pulp quality. When lignin is removed from black liquor, it will affect mostly the chemical recovery operation and steam generation rate. Since mineral acid is used to precipitate the lignin, impacts on the mill chemical balance are also expected. A great advantage of processing the wood residues for additional income results from the fact that the pulping process, pulp quality and sales are not harmfully affected. For pulp mills interested in implementing the concept of multi-products biorefinery, this work has indicated possible impacts to be considered in a technical feasibility study.