Feasibility study for acidic biorefinery concept

The integration a recovery process for spent sulfite liquor from a sulfite cooking process with a kraft pulp mill was studied in this thesis work. The process includes a fermentation process for the production of biofuel. The calculation for three cases was done. The three cases considered were with a spruce sulfite pulp production of 100, 250 and 1000 Adt/day corresponding to 10, 25 and 100% of the total pulp production. A kraft cooking process with prehydrolysis was taken in consideration as reference. Compared to kraft cooking with prehydrolysis a bigger amount of ethanol can be produced by sulfite cooking. In the kraft prehydrolysis case 40 t/day of ethanol and 1000 Adt/day pine pulp is produced and in the sulfite case the production is 113 t/day of ethanol and 1000 Adt/day of spruce pulp. The energy consumption in the sulfite process is assumed to be slightly higher than in the kraft prehydrolysis process. The recovery system for spent liquor mix was studied. The evaporation of the spent cooking liquors should be done separately. The approximately composition of melt was calculated. A comparison of all four cases was done and profitability was estimated.

Roal Oy:n käyttöhyödykejärjestelmän arviointi, optimointi ja raportointi

Prosessiteollisuudessa tarvitaan usein erilaisia apujärjestelmiä pääprosessin tueksi. Tyypillisiä tällaisia järjestelmiä ovat jäähdytys-, höyry- ja ilmajärjestelmät. Hyödykejärjestelmien kehitys jää helposti pääprosessin varjoon, joka usein johtaa tarpeettoman suuriin hyödykekustannuksiin ja järjestelmien teknisen tilan laskuun. Työn kirjallisuusosassa käsitellään Roal Oy:n fermentointiprosessin kannalta olennaisimpia hyödykevaatimuksia, niiden laskennallista ilmaisua ja vuorovaikutuksia sekä PINCH-menetelmää lämpöenergian hyötykäyttöön. Jäähdytysjärjestelmän osalta käydään läpi merkittävimmät laitetekniset ratkaisut, jäähdytystorni ja lämpöpumppu, toimintaperiaatteineen sekä luonnonvesien käyttö jäähdytykseen. Työn soveltavassa osassa seurattiin Aspergillus, Trichoderma ja Bacillus fermentointeja, joiden pohjalta luotiin kasvatuskohtainen empiirinen malli jäähdytystarpeen arviointiin perustuen sekoitustehoon, kasvatuksen hiilidioksidituottoon ja haihtumisen vaikutukseen. Kasvatuksien aikana seurattiin myös tilavuusperusteista lämmönsiirtokerrointa. Mitattujen lämmönsiirtokertoimien perustella laskettiin ominaislämmöntuottoon perustuva maksimilämpötila käytettävälle jäähdytysvedelle ja fermentorien maksimitilavuudet tunnetuilla kasvatusparametreilla eri lämpöisille jäähdytysvesille. Soveltavassa osassa käydään myös läpi Roalin höyry- ja kuumavesikulutukset ja tärkeimmät käyttökohteet. Mittaustulosten ja mallien perusteella on tehtiin kehitysehdotukset hyödykejärjestelmän optimoimiseksi.

Hydrogen production from cassava processing wastewater in an anaerobic fixed bed reactor with bamboo as a support material

Attempting to associate waste treatment to the production of clean and renewable energy, this research sought to evaluate the biological production of hydrogen using wastewater from the cassava starch treatment industry, generated during the processes of extraction and purification of starch. This experiment was carried out in a continuous anaerobic reactor with a working volume of 3L, with bamboo stems as the support medium. The system was operated at a temperature of 36°C, an initial pH of 6.0 and under variations of organic load. The highest rate of hydrogen production, of 1.1 L.d-1.L-1, was obtained with application of an organic loading rate of 35 g.L-1.d-1, in terms of total sugar content and hydraulic retention time of 3h, with a prevalence of butyric and acetic acids as final products of the fermentation process. Low C/N ratios contributed to the excessive growth of the biomass, causing a reduction of up to 35% in hydrogen production, low percentages of H2 and high concentrations of CO2in the biogas.

Developing Service-based Solutions for Water Treatment in Finnish Mining Industry

The aim of this master’s thesis is to analyze the mining industry customers' current and future needs for the water treatment services and discover new business development opportunities in the context of mine water treatment. In addition, the study focuses on specifying service offerings needed and evaluate suitable revenue generation models for them. The main research question of the study is: What kind of service needs related to water treatment can be identified in the Finnish mining industry? The literature examined in the study focused on industrial service classification and new service development process as well as the revenue generation of services. A qualitative research approach employing a case study method was chosen for the study. The present study uses customer and expert interviews as primary data source, complemented by archival data. The primary data was gathered by organizing total of 13 interviews, and the interviews were analyzed by using qualitative content analysis. The abductive-logic was chosen as the way of conducting scientific reasoning in this study. As a result, new service proposals were developed for Finnish mine industry suppliers. The main areas of development were on asset efficiency services and process support services. The service needs were strongly associated with suppliers’ know-how of water treatment process optimization, cost-effectiveness as well as on alternative technologies. The study provides an insight for managers that wish to pursue a water treatment services as a part of their business offering.

Työkoneiden dieselmoottoreiden hyötysuhteen parantaminen lämmöntalteenoton avulla

Tämä diplomityö on osa Lappeenrannan teknillisessä yliopistossa tehtävää tutkimusta polttomoottoreiden energiatehokkuuden parantamisessa. Työn tavoitteena on saada tutkimustietoa polttomoottoreiden hukkalämpövirtojen hyödyntämisestä sähköntuotannossa. Tavoitteena on muodostaa näkemys Mikro-ORC energiamuuntimen mahdollisuuksista ja reunaehdoista osana työkoneluokan (150 kW… 400 kW) dieselmoottorikokonaisuutta, erityisesti maataloussektorilla. Työssä tarkasteltaviksi moottoreiksi valittiin kaksi eri AGCO Sisu Powerin dieselmoottoria. Laskennat suoritettiin moottorin valmistajan antamien hukkalämpövirtojen arvojen perusteella. Laskennan perusperiaatteena oli tutkia ORC-prosessin tuottamaa lisäsähkötehoa hyödyntämällä pakokaasujen lämpöenergiaa korkea-, keski- ja matalalämpötiloissa. Työssä vertailtiin kahden eri kiertoaineen prosessihyötysuhdetta, saatava sähkötehoa sekä prosessin sisäisiä parametreja. Lisäksi työssä tutkittiin ORC-prosessin laskentaa suunnittelupisteessä (design) ja suunnittelupisteen ulkopuolella (off-design), prosessisuureiden optimointia ja lämmönsiirtimien mitoitusta. Diplomityössä tarkasteltiin moottorin energiataseen mukaisten arvojen lisäksi moottorin parametrien muuttamisen vaikutusta hukkalämpövirroista saatavan tehoon. Työssä saatiin arvokasta tietoa polttomoottoreiden hukkalämpövirtojen muuntamisesta sähköksi ORC:lla sekä moottorin energiatehokkuuden parantamisesta.

Biomassahydrolysaattien puhdistus uutolla

Lignoselluloosasta koostuvasta biomassasta valmistetaan hydrolysoimalla sokereita, jotka jatkojalostetaan fermentoimalla bioetanoliksi. Bioetanolia käytetään fossiilisten polttoaineiden korvaajana esimerkiksi ajoneuvoissa. Bioetanolin valmistuksessa pyritään mahdollisimman hyvään saantoon, jotta sen valmistus olisi taloudellisesti kannattavaa. Hydrolyysin aikana syntyy sokerien lisäksi orgaanisia happoja, furaanin johdannaisia sekä fenolisia yhdisteitä. Yleisimpiä syntyviä yhdisteitä ovat muun muassa etikkahappo, furfuraali ja hydroksimetyylifurfuraali. Nämä yhdisteet haittaavat sokerien fermentointiprosessia ja pienentävät etanolin saantoa. Fermentointiprosessia haittaavien yhdisteiden poistoon hydrolysaattiliuoksesta voidaan käyttää esimerkiksi haihdutusta, membraanierotusta, adsorptiota, saostusta, sekä uuttoa. Tämän työn tarkoituksena oli tutkia leikkaussekoittimen soveltuvuutta biomassahydrolysaatin epäpuhtauksien erotukseen. Lisäksi kirjallisuusosassa on esitetty hydrolysointiprosessissa syntyviä haitta-aineita ja niiden erotusmenetelmiä.

Ionic liquid mediated biomass deconstruction: from analysis challenges to fermentable sugars

Ionic liquids, ILs, have recently been studied with accelerating interest to be used for a deconstruction/fractionation, dissolution or pretreatment processing method of lignocellulosic biomass. ILs are usually utilized combined with heat. Regarding lignocellulosic recalcitrance toward fractionation and IL utilization, most of the studies concern IL utilization in the biomass fermentation process prior to the enzymatic hydrolysis step. It has been demonstrated that IL-pretreatment gives more efficient hydrolysis of the biomass polysaccharides than enzymatic hydrolysis alone. Both cellulose (especially cellulose) and lignin are very resistant towards fractionation and even dissolution methods. As an example, it can be mentioned that softwood, hardwood and grass-type plant species have different types of lignin structures leading to the fact that softwood lignin (guaiacyl lignin dominates) is the most difficult to solubilize or chemically disrupt. In addition to the known conventional biomass processing methods, several ILs have also been found to efficiently dissolve either cellulose and/or wood samples – different ILs are suitable for different purposes. An IL treatment of wood usually results in non-fibrous pulp, where lignin is not efficiently separated and wood components are selectively precipitated, as cellulose is not soluble or degradable in ionic liquids under mild conditions. Nevertheless, new ILs capable of rather good fractionation performance have recently emerged. The capability of the IL to dissolve or deconstruct wood or cellulose depends on several factors, (e.g. sample origin, the particle size of the biomass, mechanical treatments as pulverization, initial biomassto-IL ratio, water content of the biomass, possible impurities of IL, reaction conditions, temperature etc). The aim of this study was to obtain (fermentable) saccharides and other valuable chemicals from wood by a combined heat and IL-treatment. Thermal treatments alone contribute to the degradation of polysaccharides (e.g. 150 °C alone is said to cause the degradation of polysaccharides), thus temperatures below that should be used, if the research interest lies on the IL effectiveness. On the other hand, the efficiency of the IL-treatment can also be enhanced to combine other treatment methods, (e.g. microwave heating). The samples of spruce, pine and birch sawdust were treated with either 1-Ethyl-3-methylimidazolium chloride, Emim Cl, or 1-Ethyl-3-methylimidazolium acetate, Emim Ac, (or with ionized water for comparison) at various temperatures (where focus was between 80 and 120 °C). The samples were withdrawn at fixed time intervals (the main interest treatment time area lied between 0 and 100 hours). Double experiments were executed. The selected mono- and disaccharides, as well as their known degradation products, 5-hydroxymethylfurfural, 5-HMF, and furfural were analyzed with capillary electrophoresis, CE, and high-performance liquid chromatography, HPLC. Initially, even GC and GC-MS were utilized. Galactose, glucose, mannose and xylose were the main monosaccharides that were present in the wood samples exposed to ILs at elevated temperatures; in addition, furfural and 5-HMF were detected; moreover, the quantitative amount of the two latter ones were naturally increasing in line with the heating time or the IL:wood ratio.

Lean Innovation in Large Companies: a Case of Implementation in R&D

The main objective of the study is to evaluate the impact of Lean Innovation management philosophy on the creativity potential of the large multinational enterprise. A theory of Lean Innovation indicates that the modern company in any industry can successfully combine both waste-decreasing approach and innovative potential promotion through creativity cultivation or, at least, preservation. The theoretical part of the work covers the main factors, pros and cons of Lean thinking and Innovation management separately, along with generalized new product development overview. While the modern international market becomes more accessible for entrepreneural initiatives, small enterprises and start-ups, large international corporations are more subject to adopt the Lean Innovation approach in both operational and product development sectors due to extended resources and capabilities. Moreover, a multinational enterprise is a highly probable pioneer in Lean innovation implementation. The empirical part of the thesis refers to a case of large European enterprise, operating in many markets around the globe, that currently undergoes innovation management adjustments and implementations in product development while already have related themselves with operational process optimization process through Lean thinking. A goal of the work is to understand what kind of difficulties and consequences a large international firm faces when dealing with Lean Innovation to improve own performance, if they can be sealed for generalized approach.

Sinkityslinjan pesuosan optimointi

Työn tavoitteena oli sinkityslinjan pesuosan toiminnan optimointi. Teoriakatsauksen ja haastattelututkimusten avulla työssä selvitettiin, mitkä tekijät pesuosalla tai teräsnauhan pesua edeltävissä prosessivaiheissa vaikuttavat pesutehoon alentavasti. Pesuosan ajoparametrien muutoskokeiden avulla määritettiin kunkin pesuparametrin suhteellinen vaikutus pesutulokseen sekä pesuosan optimaaliset ajoparametrit. Vaikutuksia arvioitiin pinnanpuhtauden ja pesuvesien laboratorioanalyysien sekä prosessidatan avulla. Jätevesianalyysien ja prosessidatan avulla arvioitiin lisäksi pesuosan muutosten vaikutusta pesusta syntyviä jätevesiä käsittelevän jätevesilaitoksen toimintaan. Laitetestauksen avulla työssä kartoitettiin, mikä menetelmä pinnanpuhtauden määrittämiseen soveltuu pesuosalle parhaiten. Kustannusarvioinnilla selvitettiin, millä toimin pesuosan toimintavarmuutta on edullisinta ylläpitää. Työn tulosten pohjalta lämpötilalla todettiin olevan pesutuloksen kannalta merkittävin vaikutus. Sen sijaan kemikaaliannostelun merkitys oli vähäinen. Vesien säännöllisen uudistamisen todettiin olevan olennainen pesuvesien ylläpitokeino nykyisessä pesutilanteessa. Se todettiin lisäksi ennakoivana toimenpiteenä kannattavammaksi kuin pesuosan täystyhjäykset ongelmatilanteissa. Teippitestein määritettävälle pinnanpuhtaudelle katsottiin sopivaksi vaihteluväliksi 40–75 %. Työssä todettiin, että pesua edeltävän kylmävalssin valssiöljyn vaihto sekä valssilla tuotetun teräsnauhan pinnanpuhtaus vaikuttavat merkittävästi pesuosan toimintakykyyn ja pesuosan pyörittämisestä aiheutuviin kustannuksiin. Toimenpiteet pesuosalla vaikuttavat lisäksi jätevesilaitoksen käsittelyvaatimuksiin, joskin myös tasaavat sen toimintaa. Työssä ehdotettiin ratkaisukeinoja pesuosan toimintavarmuuden varmistamiseksi jatkossa, sekä tarjottiin työkaluja, joiden avulla tulevissa investointipäätöksissä voidaan ottaa huomioon myös pesuosan toiminnan edellytykset.

STATISTICAL ANALYSYS OF THE SCFE OF A BRAZILAN MINERAL COAL

The influence of some process variables on the productivity of the fractions (liquid yield times fraction percent) obtained from SCFE of a Brazilian mineral coal using isopropanol and ethanol as primary solvents is analyzed using statistical techniques. A full factorial 23 experimental design was adopted to investigate the effects of process variables (temperature, pressure and cosolvent concentration) on the extraction products. The extracts were analyzed by the Preparative Liquid Chromatography-8 fractions method (PLC-8), a reliable, non destructive solvent fractionation method, especially developed for coal-derived liquids. Empirical statistical modeling was carried out in order to reproduce the experimental data. Correlations obtained were always greater than 0.98. Four specific process criteria were used to allow process optimization. Results obtained show that it is not possible to maximize both extract productivity and purity (through the minimization of heavy fraction content) simultaneously by manipulating the mentioned process variables.

Application of protein-phenolic based coating on tomatoes (Lycopersicum esculentum)

The aim of this study was to investigate the use of protein-phenolic based coating made from fermented rice bran on cherry tomatoes (Lycopersicum esculentum). Tests were performed with glycerol 3% (v/v), glycerol with protein-phenolic rice bran extract (5%), glycerol with protein-phenolic extract after 96 hours of fermentation (5%), and a control (without coating). The coated cherry tomatoes were kept at room temperature for 28 days. Mass loss, pH and acidity, total soluble solids, and carotenoids were determined every 96 hours. The coating made from the biomass extract reduced the carotenoid and acidity levels in the fruits studied by 17 and 21.1%, respectively, compared to the control. The coating proved an efficient barrier to water vapor with mass loss of 57% less than the control suggesting that it can be used as an alternative for vegetable tissue conservation.

An artificial neural network model for prediction of quality characteristics of apples during convective dehydration

In this study, the effects of hot-air drying conditions on color, water holding capacity, and total phenolic content of dried apple were investigated using artificial neural network as an intelligent modeling system. After that, a genetic algorithm was used to optimize the drying conditions. Apples were dried at different temperatures (40, 60, and 80 °C) and at three air flow-rates (0.5, 1, and 1.5 m/s). Applying the leave-one-out cross validation methodology, simulated and experimental data were in good agreement presenting an error < 2.4 %. Quality index optimal values were found at 62.9 °C and 1.0 m/s using genetic algorithm.

Screening and kinetics of glutaminase and glutamate decarboxylase producing lactic acid bacteria from fermented Thai foods

L-glutaminase and glutamic acid decarboxylase (GAD) catalyzes the hydrolysis of L-glutamine and glutamate, respectively. L-glutaminase widely used in cancer therapy along with a combination of other enzymes and most importantly these enzymes were used in food industries, as a major catalyst of bioconversion. The current investigation was aimed to screen and select L-glutaminase, and GAD producing lactic acid bacteria (LAB). A total of 338 LAB were isolated from fermented meat, fermented fish, fermented soya bean, fermented vegetables and fruits. Among 338 isolates, 22 and 237 LAB has been found to be positive for L-glutaminase and GAD, respectively. We found that 30 days of incubation at 35 ºC and pH 6.0 was the optimum condition for glutaminase activity by G507/1. G254/2 was found to be the best for GAD activity with the optimum condition of pH 6.5, temperature 40 ºC and ten days of incubation. These LAB strains, G507/1 and G254/2, were identified as close relative of Lactobacillus brevis ATCC 14869 and Lactobacillus fermentum NBRC 3956, respectively by 16S rRNA sequencing. Further, improvements in up-stream of the fermentation process with these LAB strains are currently under development.

Characterization of polyphenol oxidase in two cocoa (Theobroma cacao L.) cultivars produced in the south of Bahia, Brazil

Abstract The reactions leading to the formation of precursors of chocolate flavor are performed by endogenous enzymes present in the cocoa seed. Polyphenol oxidase (PPO) presence and activity during fermentation of cocoa beans is responsible for the development of flavor precursors and is also implicated in the reduction of bitterness and astringency. However, the reliability of cocoa enzyme activities is complicated due to variations in different genotypes, geographical origins and methods of fermentation. In addition, there is still a lack of systematic studies comparing different cocoa cultivars. So, the present study was designed to characterize the activity of PPO in the pulp and seeds of two cocoa cultivars, PH 16 and TSH 1188. The PPO activity was determined spectrophotometrically and characterized as the optimal substrate concentration, pH and temperature and the results were correlated with the conditions during the fermentation process. The results showed the specificity and differences between the two cocoa cultivars and between the pulp and seeds of each cultivar. It is suggested that specific criteria must be adopted for each cultivar, based on the optimal PPO parameters, to prolong the period of maximum PPO activity during fermentation, contributing to the improvement of the quality of cocoa beans.

Improvements in Fermentative Hydrogen Production through Physiological Manipulation and Metabolic Engineering

La production biologique d'hydrogène (H2) représente une technologie possible pour la production à grande échelle durable de H2 nécessaire pour l'économie future de l'hydrogène. Cependant, l'obstacle majeur à l'élaboration d'un processus pratique a été la faiblesse des rendements qui sont obtenus, généralement autour de 25%, bien en sous des rendements pouvant être atteints pour la production de biocarburants à partir d'autres processus. L'objectif de cette thèse était de tenter d'améliorer la production d'H2 par la manipulation physiologique et le génie métabolique. Une hypothèse qui a été étudiée était que la production d'H2 pourrait être améliorée et rendue plus économique en utilisant un procédé de fermentation microaérobie sombre car cela pourrait fournir la puissance supplémentaire nécessaire pour une conversion plus complète du substrat et donc une production plus grande d'H2 sans l'aide de l'énergie lumineuse. Les concentrations optimales d’O2 pour la production de H2 microaérobie ont été examinées ainsi que l'impact des sources de carbone et d'azote sur le processus. La recherche présentée ici a démontré la capacité de Rhodobacter capsulatus JP91 hup- (un mutant déficient d’absorption-hydrogénase) de produire de l'H2 sous condition microaérobie sombre avec une limitation dans des quantités d’O2 et d'azote fixé. D'autres travaux devraient être entrepris pour augmenter les rendements d'H2 en utilisant cette technologie. De plus, un processus de photofermentation a été créé pour améliorer le rendement d’H2 à partir du glucose à l'aide de R. capsulatus JP91 hup- soit en mode non renouvelé (batch) et / ou en conditions de culture en continu. Certains défis techniques ont été surmontés en mettant en place des conditions adéquates de fonctionnement pour un rendement accru d'H2. Un rendement maximal de 3,3 mols de H2/ mol de glucose a été trouvé pour les cultures en batch tandis que pour les cultures en continu, il était de 10,3 mols H2/ mol de glucose, beaucoup plus élevé que celui rapporté antérieurement et proche de la valeur maximale théorique de 12 mols H2/ mol de glucose. Dans les cultures en batch l'efficacité maximale de conversion d’énergie lumineuse était de 0,7% alors qu'elle était de 1,34% dans les cultures en continu avec un rendement de conversion maximum de la valeur de chauffage du glucose de 91,14%. Diverses autres approches pour l'augmentation des rendements des processus de photofermentation sont proposées. Les résultats globaux indiquent qu'un processus photofermentatif efficace de production d'H2 à partir du glucose en une seule étape avec des cultures en continu dans des photobioréacteurs pourrait être développé ce qui serait un processus beaucoup plus prometteur que les processus en deux étapes ou avec les co-cultures étudiés antérieurément. En outre, l'expression hétérologue d’hydrogenase a été utilisée comme une stratégie d'ingénierie métabolique afin d'améliorer la production d'H2 par fermentation. La capacité d'exprimer une hydrogénase d'une espèce avec des gènes de maturation d'une autre espèce a été examinée. Une stratégie a démontré que la protéine HydA orpheline de R. rubrum est fonctionnelle et active lorsque co-exprimée chez Escherichia coli avec HydE, HydF et HydG provenant d'organisme différent. La co-expression des gènes [FeFe]-hydrogénase structurels et de maturation dans des micro-organismes qui n'ont pas une [FeFe]-hydrogénase indigène peut entraîner le succès dans l'assemblage et la biosynthèse d'hydrogénase active. Toutefois, d'autres facteurs peuvent être nécessaires pour obtenir des rendements considérablement augmentés en protéines ainsi que l'activité spécifique des hydrogénases recombinantes. Une autre stratégie a consisté à surexprimer une [FeFe]-hydrogénase très active dans une souche hôte de E. coli. L'expression d'une hydrogénase qui peut interagir directement avec le NADPH est souhaitable car cela, plutôt que de la ferrédoxine réduite, est naturellement produit par le métabolisme. Toutefois, la maturation de ce type d'hydrogénase chez E. coli n'a pas été rapportée auparavant. L'opéron hnd (hndA, B, C, D) de Desulfovibrio fructosovorans code pour une [FeFe]-hydrogénase NADP-dépendante, a été exprimé dans différentes souches d’E. coli avec les gènes de maturation hydE, hydF et hydG de Clostridium acetobutylicum. L'activité de l'hydrogénase a été détectée in vitro, donc une NADP-dépendante [FeFe]-hydrogénase multimérique active a été exprimée avec succès chez E. coli pour la première fois. Les recherches futures pourraient conduire à l'expression de cette enzyme chez les souches de E. coli qui produisent plus de NADPH, ouvrant la voie à une augmentation des rendements d'hydrogène via la voie des pentoses phosphates.