The loss of efficiency and performance of bioprocesses on scale-up is well known, but not fully understood. This work addresses this problem, by studying the effect of some fermentation gradients (pH, glucose and oxygen) at a larger scale in a bench-scale two compartment reactor (PFR + STR) using the cadaverine-producing recombinant bacterium, Corynebacterium glutamicum DM1945 Δact3 Ptuf-ldcC_OPT. The initial scale down strategy increased the magnitude of these gradients by only increasing the mean cell residence time in the plug flow reactor (τ_PFR). The cell growth and product related rate constants were compared as the τ_PFR was increased; differences were significant in some cases, but only up to 2 min residence time. For example, losses in cadaverine productivity when compared to the control fed-batch fermentation on average for the τ_PFR of 1 min, 2 min and 5 min were 25 %, 42 % and 46 % respectively. This indicated that the increasing the τ_PFR alone does not necessarily increase the magnitude of fermentation gradients. The new scale-down strategy developed here, increased the magnitude of fermentation gradients by not only increasing the τ_PFR, but also considering the mean frequency at which the bacterial cells entered the PFR section (f_m). The f_m was kept constant by reducing the broth volume in the STR. Hence, the bacterial cells also spent shorter times in the well mixed STR, as the τ_PFR was increased (hypothesised as giving the bacterial cells less time to recover the non-ideal PFR section of the SDR). On adoption of this strategy cadaverine productivity decreases for the τ_PFR of 1 min, 2 min and 5 min were 25 %, 32 % and 53 % respectively. Thus, highlighting that loss in performance is most likely to occur as the magnitude of heterogeneity within the fermentation environment increases. However, Corynebacterium glutamicum DM1945 Δact3 Ptuf-ldcC_OPT did show some resilience in its biomass productivity. It was only marginally affected in the harshest of conditions simulated here.

Le travail de cette thèse a permis tout d’abord d’aboutir à un protocole simplifié pour la synthèse des p-tert-butylcalix[7] et [9]arènes, composés jusqu’à lors difficilement préparables. Ces macrocycles ont été obtenus en grosse quantité, de l’ordre de la dizaine de gramme. Il faut également noter que cette synthèse sur grande échelle permet d’obtenir les p-tert-butylcalix[10] et [12]arènes avec des rendements modestes mais une simplicité remarquable. A partir de ces calixarènes, deux voies principales de per-fonctionnalisation ont été mises en oeuvre : La réaction de Williamson, consistant à former des éthers, et l’estérification via l’utilisation d’anhydrides. Au total, ce sont 10 nouveaux calixarènes fonctionnalisés qui ont été obtenus. Le comportement dynamique et conformationnel des calix[9]arènes originaux a été évalué en solution et à l’état solide. Dans le cas où cela a été possible, la détermination des constantes de vitesse et d’énergie libre des mouvements conformationnels a montré que ces calix[9]arènes fonctionnalisés étaient très mobiles. En outre, trois nouvelles structures RX ont été obtenues et ont confirmé que ces macrocycles adoptaient une conformation désordonnée. En l’état, ces nouveaux calixarènes ne sont pas des candidats de choix pour devenir des hôtes moléculaires efficaces. Toutefois, ce travail a permis d’améliorer nos connaissances sur des structures dérivées de p-tert-butylcalix[n]arènes (n = 7, 9, 10 et 12) peu étudiés jusqu’à présent / The work of this thesis allowed to propose a simplified procedure for the synthesis of p-tertbutylcalix[ 7] and [9]arenes, which were hardly synthesizable until now. Those macrocycles were obtained in a large amount, about a dozen of grams. It’s important to emphasize that this large scale synthesis allow to obtain the p-tert-butylcalix[10] and [12]arenes with moderate yields but in a straight and simple procedure. From these calixarenes, two main ways of per-functionalization were attempted: Williamson reaction, consisting in forming ethers and esterification by using anhydrides. Totally, 10 new functionalized calixarenes were obtained. Their dynamic and conformational behaviors in solution as well as in the solid state were explored. The determination of the rate constants and of the free energy barrier of the conformational motion has shown that those compounds were mobile. Moreover, three original X-Ray structures were obtained and have revealed that those macrocycles adopted a disordered conformation. At this point, those new calixarenes are not well designed to act as efficient molecular host. However, this work allowed to improve our knowledges on structures made from the p-tert-butylcalix[n]arene (n = 7, 9, 10 and 12), a skeleton rarely described and studied up to now

Roll compaction is a continuous process commonly used in the pharmaceutical industry for dry granulation of moisture and heat sensitive powder blends. It is intended to increase bulk density and improve flowability. Roll compaction is a complex process that depends on many factors, such as feed powder properties, processing conditions and system layout. Some of the variability in the process remains unexplained. Accordingly, modeling tools are needed to understand the properties and the interrelations between raw materials, process parameters and the quality of the product. It is important to look at the whole manufacturing chain from raw materials to tablet properties. The main objective of this thesis was to investigate the impact of raw materials, process parameters and system design variations on the quality of intermediate and final roll compaction products, as well as their interrelations. In order to do so, we have conducted a series of systematic experimental studies and utilized chemometric tools, such as design of experiments, latent variable models (i.e. PCA, OPLS and O2PLS) as well as mechanistic models based on the rolling theory of granular solids developed by Johanson (1965). More specifically, we have developed a modeling approach to elucidate the influence of different brittle filler qualities of mannitol and dicalcium phosphate and their physical properties (i.e. flowability, particle size and compactability) on intermediate and final product quality. This approach allows the possibility of introducing new fillers without additional experiments, provided that they are within the previously mapped design space. Additionally, this approach is generic and could be extended beyond fillers. Furthermore, in contrast to many other materials, the results revealed that some qualities of the investigated fillers demonstrated improved compactability following roll compaction. In one study, we identified the design space for a roll compaction process using a risk-based approach. The influence of process parameters (i.e. roll force, roll speed, roll gap and milling screen size) on different ribbon, granule and tablet properties was evaluated. In another study, we demonstrated the significant added value of the combination of near-infrared chemical imaging, texture analysis and multivariate methods in the quality assessment of the intermediate and final roll compaction products. Finally, we have also studied the roll compaction of an intermediate drug load formulation at different scales and using roll compactors with different feed screw mechanisms (i.e. horizontal and vertical). The horizontal feed screw roll compactor was also equipped with an instrumented roll technology allowing the measurement of normal stress on ribbon. Ribbon porosity was primarily found to be a function of normal stress, exhibiting a quadratic relationship. A similar quadratic relationship was also observed between roll force and ribbon porosity of the vertically fed roll compactor. A combination of design of experiments, latent variable and mechanistic models led to a better understanding of the critical process parameters and showed that scale up/transfer between equipment is feasible.

The objectives of this project were to survey the flotation circuit of the Boliden concentrator, mass balance collected data and evaluate a scale-up model for laboratory flotation results. The model assumes that half of the recovery to cleaner middlings in a standard laboratory test would report to the final concentrate if it were done in closed circuit, as is the case in a full-scale plant. It has been used by Boliden Mineral AB since 1982 but its accuracy had not been studied since 1986. The model can be categorised as of open circuit type with scale-up factors. The project was based on a complex Ag-Au-Cu-Pb-Zn sulphide ore from the Kristineberg mine. Laboratory tests were done to produce concentrates of CuPb, Cu, Pb and Zn with pulp samples from the concentrator as feed material. The software HSC 9.3 was used to mass balance data from the plant survey. It was decided that the model would be deemed usable if it was able to predict the plant results with the same accuracy as in the survey of 1986. A simulated locked cycle test with split factors (Agar & Kipkie, 1978) was identified as an alternative scale-up model. The results showed that the model was able to predict the plant results with the same accuracy as in 1986. It was especially good at predicting grade and recovery of the main element in a concentrate. For example, it predicted an 18 % higher grade and 11 % lower recovery of Cu to the CuPb concentrate, while a 3 % lower grade and 11 % lower recovery of Zn was predicted to the Zn concentrate. The locked cycle model gave much worse predictions on grades, but more accurate recoveries. It was also better at predicting the behaviour of minor impurity elements such as As and Bi. A recommendation is to combine the two alternatives in a type of "mixed cycle" model. In this study, it would have predicted an 18 % higher grade and 7 % lower recovery of Cu to the CuPb concentrate, as well as a 3 % lower grade and 1 % higher recovery of Zn to the Zn concentrate compared with plant results. Such a model seems to give better figures, but should be put to the test on more samples and ores to confirm this belief. It could at the very least be used to check the reliability of results predicted by the current scale-up model. / Syftet med det här examensarbetet var att utföra en detaljprovtagning av flotationskretsen i Bolidens anrikningsverk, massbalansera data och sedan utvärdera en modell för uppskalning av resultat från laboratorieflotationer. Modellen antar att hälften av utbytet till returgodset i ett satsvis laboratorieförsök skulle rapportera till det slutliga koncentratet om det återcirkulerades, såsom i ett anrikningsverk. Den har använts av Boliden Mineral AB sedan 1982 men utvärderades senast 1986. Kategoriskt kan den ses som en uppskalningsmodell av typen öppen krets med skalfaktorer. Projektet baserades på en komplex Ag-Au-Cu-Pb-Zn sulfidmalm från gruvan i Kristineberg. Laboratorieförsök utfördes för att ta fram koncentrat av CuPb, Cu, Pb och Zn, med pulpprover från driften som utgångsmaterial. Programmet HSC 9.3 användes för att massbalansera datan från provtagningen. Det bestämdes att modellen skulle anses som godtagbar ifall den kunde förutspå driftresultatet med samma noggrannhet som 1986. Ett simulerat försök av typen sluten krets (Agar & Kipkie, 1978) identifierades som den mest intressanta alternativmodellen och även den utvärderades. Resultaten visade att modellen än idag ger godtagbara förutsägelser med samma noggrannhet som 1986. Modellen var särskilt bra på att förutspå halt och utbyte av den huvudsakliga metallen till dess eget koncentrat. Den förutspådde exempelvis en 18 % högre halt och 11 % lägre utbyte av Cu till CuPb-koncentratet, samt 3 % lägre halt och 11 % lägre utbyte av Zn till Zn-koncentratet. Den alternativa modellen gav sämre förutsägelser med avseende på halter, men bättre med avseende på utbyten. Den var bättre på att förutspå beteendet hos låghaltiga föroreningar såsom As och Bi. Rekommendationen är att kombinera de två modellerna till en "blandkretsmodell". I den här undersökningen hade ett sådant alternativ förutspått en 18 % högre halt och 7 % lägre utbyte av Cu till CuPb-koncentratet, samt 3 % lägre halt och 1 % högre utbyte av Zn till Zn-koncentratet jämfört med driftresultatet. En sådan modell tycks ge bättre förutsägelser, men bör testas på fler prover och malmtyper. Den borde åtminstone kunna användas för att kontrollera trovärdigheten hos resultaten förutspådda av den nuvarande modellen.

Abstract Electrocoagulation (EC) is an emerging technology that combines the functions and advantages of conventional coagulation, flotation, and electrochemistry in water and wastewater treatment. The aims of this work included doing an updated literary review of recent feasible applications of EC, which were found to be plentiful. Since the economic and practical operational key figures related to EC haven’t been extensively mapped out before, this was a prime objective of this part of the work. The aim of the next part of this work was to find new feasible applications for EC in the treatment of water and wastewater. The studied wastewaters included bio- and synthetic oil-in-water emulsions, various industrial nutrient-containing wastewaters, and peat bog drainage water containing humic substances (an interesting and topical problem, especially in Finland). These studies proved the feasibility of EC. In addition, larger-scale experiments were also conducted successfully, thus proving the scalability of the EC process. Extensive economic analyses of the studied EC applications were also done. The operational costs and energy consumption of EC were found to be very low—typically about 0.1–1.0 €/m3 and 0.4–4.0 kWh/m3. It has been forecasted that in the future there will be a shortage of virgin phosphorus. Therefore, another essential purpose of this work was to conduct a preliminary study on the feasibility of using EC for nutrient (especially phosphorus, but also nitrogen) removal and recovery from different types of real wastewater. Specifically, it may be possible to use EC sludges containing notable amounts of phosphorus and nitrogen as additives in granulated bio ash-based fertilizer products for various applications. This is a novel idea and a “hot topic” in the waste utilization sector and in circular and bioeconomy. / Tiivistelmä Elektrokoagulaatio (electrocoagulation, EC) on nosteessa oleva teknologia, joka yhdistää perinteisen koagulaation, flotaation ja sähkökemian hyödyt ja mahdollisuudet vesien ja jätevesien käsittelyssä. Tämän työn ensimmäisenä tavoitteena oli laatia kirjallisuuskatsaus EC:n viimeaikaisista käyttökelpoisista sovelluksista, joita löytyi runsaasti. Koska EC:n toiminnallisia ja taloudellisia avainlukuja ei ole kartoitettu kattavasti aiemmin, tämän tekeminen oli tämän osion tärkein tavoite. Väitöstyön seuraavana tavoitteena oli löytää uusia sovellutuksia EC:lle vesien ja jätevesien käsittelyssä. Tutkittuja vesiä olivat bio- ja synteettisistä öljyistä valmistetut öljy-vesiemulsiot, erilaiset teolliset ravinnepitoiset jätevedet ja humusainepitoiset turvesoiden valumavedet (kiinnostava ja ajankohtainen ongelma, erityisesti Suomessa). EC todettiin käyttökelpoiseksi teknologiaksi näissä kokeissa. Suuremman skaalan kokeilla todistettiin lisäksi EC-prosessin skaalautuvuus. Lisäksi, em. EC-sovellutuksista suoritettiin kattavat taloudelliset analyysit. EC:n käyttökustannukset ja energiankulutus todettiin erittäin pieniksi, tyypillisesti ne olivat välillä 0.1–1.0 €/m3 ja 0.4–4.0 kWh/m3. On ennustettu, että tulevaisuudessa on pulaa neitseellisestä fosforista. Tästä johtuen eräs tämän työn keskeisistä tarkoituksista oli suorittaa alustavia kokeita liittyen EC:n käyttökelpoisuuteen ravinteiden (erityisesti fosfori, mutta myös typpi) poistossa ja talteenotossa aidoista jätevesistä. Erityisesti jatkossa voisi olla järkevää hyödyntää runsaasti fosforia ja typpeä sisältäviä EC-sakkoja lisäaineina rakeistetuissa biotuhkapohjaisissa lannoitteissa eri sovellutuksissa. Tämä idea on uusi ja on jo herättänyt suurta kiinnostusta mm. kierto- ja biotaloussektoreilla.

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The objective of this thesis was to study problems of an insufficient database processing performance and possibilities how to improve the performance with database configuration file optimizations, more powerful hardware and parallel processing. The master thesis contains a description of relational databases, storage media and different forms of parallelism with its use in database systems. There is a description of the developed software for testing database performance. The program was used for testing several database configuration files, various hardware, different database systems (PostgreSQL, Oracle) and advantages of parallel method "partitioning". Test reports and evaluation results are described at the end of the thesis.