Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Research of wood fuel market in Ukraine and the Republic of Belarus

The goal of the present work was to describe the wood fuel market of Ukraine and the Republic of Belarus, to estimate wood fuel potential and to research opportunities of wood fuel trading. Nowadays the wood waste, wood residues and by-products are becoming more and more potential raw materials for energy production. Against the background of unstable prices of traditional energy sources and environmental degradation, European States are planning to get 12% of energy from alternative sources already in 2010. Wastes of wood-working and agricultural productions are such sources. At present time the most popular wood biofuels are wood pellets, briquettes, wood chips and logs. Ukraine and the Republic of Belarus have a rather big potential of wood fuel resources. But wood fuels markets of these countries are on the entry level and quite disorganized. There is almost no domestic usage of wood biofuel. All produced pellets, briquettes as well as wood chips and logs go to the export, but the volumes are not high at present time. Ukraine and the Republic of Belarus have a very suitable geographical location. The most promising directions of wood fuel trading are developed wood fuel markets of Northern countries, Austria, Germany as well as actively developing markets of Poland and Hungary. At the long distance truck and sea transportation are the most appropriate. At a short distance cheap transportation by rail is more suitable. Thereby export is a potential opportunity for development of wood fuel production and in the future for usage in the researched countries.

Inter organizational learning within and by innovation networks

The thesis deals with the phenomenon of learning between organizations in innovation networks that develop new products, services or processes. Inter organizational learning is studied especially at the level of the network. The role of the network can be seen as twofold: either the network is a context for inter organizational learning, if the learner is something else than the network (organization, group, individual), or the network itself is the learner. Innovations are regarded as a primary source of competitiveness and renewal in organizations. Networking has become increasingly common particularly because of the possibility to extend the resource base of the organization through partnerships and to concentrate on core competencies. Especially in innovation activities, networks provide the possibility to answer the complex needs of the customers faster and to share the costs and risks of the development work. Networked innovation activities are often organized in practice as distributed virtual teams, either within one organization or as cross organizational co operation. The role of technology is considered in the research mainly as an enabling tool for collaboration and learning. Learning has been recognized as one important collaborative process in networks or as a motivation for networking. It is even more important in the innovation context as an enabler of renewal, since the essence of the innovation process is creating new knowledge, processes, products and services. The thesis aims at providing enhanced understanding about the inter organizational learning phenomenon in and by innovation networks, especially concentrating on the network level. The perspectives used in the research are the theoretical viewpoints and concepts, challenges, and solutions for learning. The methods used in the study are literature reviews and empirical research carried out with semi structured interviews analyzed with qualitative content analysis. The empirical research concentrates on two different areas, firstly on the theoretical approaches to learning that are relevant to innovation networks, secondly on learning in virtual innovation teams. As a result, the research identifies insights and implications for learning in innovation networks from several viewpoints on organizational learning. Using multiple perspectives allows drawing a many sided picture of the learning phenomenon that is valuable because of the versatility and complexity of situations and challenges of learning in the context of innovation and networks. The research results also show some of the challenges of learning and possible solutions for supporting especially network level learning.

Interactions between Polyunsaturated Fatty Acids and Probiotics

The prevalence of inflammatory based diseases has increased in industrialized countries over the last decades. For allergic diseases, two primary hypotheses have been proposed to explain this phenomenon, namely the hygiene and dietary evolution based hypothesis. Particularly, the reduced early exposure to microbes and an increase in the amount of polyunsaturated fatty acids (especially n-6 PUFA) in the diet have been discussed. Often, these two factors have been studied independently, even though both factors have been shown to possess potential health benefits and their mode of action to share similar mechanisms. The hypothesis of the present study was that demonstrate that PUFA and probiotics are not separate entities as such but do interact with each other. In the present study, we investigated whether maternal diet and atopic status influence the PUFA composition of breast milk and serum fatty acids of infants, and whether the fatty acid absorption and utilization of infant formula fatty acids is affected by supplementation of infant formula with probiotic bacteria (Lactobacillus GG and Bifidobacterium lactis Bb-12). Moreover, we investigated the mechanisms by which different PUFA influence the physicochemical and functional properties of probiotics as well as functionality of epithelial cells in vitro. We demonstrated a carry-over effect of dietary fatty acids from maternal diet via breast milk into infants’ serum lipid fatty acids. Our data confirmed the previously shown allergy –related PUFA level imbalances, though it did not fully support the impaired desaturation and elongation capacity hypothesis. We also showed that PUFA incorporation into phospholipids of infants was influenced by probiotics in infant formula in a strain dependent manner. Especially,Bifidobacterium lactis Bb-12 in infant formula promoted the utilization of n-3 PUFA. Mechanistically, we demonstrated that probiotics (Lactobacillus GG, Lactobacillus casei Shirota and Lactobacillus bulgaricus) did incorporate and interconvert exogenous free PUFA in the growth medium into bacterial fatty acids strain and PUFA dependently. In general, high concentrations of free PUFA inhibited the growth and mucus adhesion of probiotics, whereas low concentrations of specific long chain PUFA were found to promote the growth and mucus adhesion of Lactobacillus casei Shirota. These effects were paralleled with only minor alterations in hydrophobicity and electron donor – electron acceptor properties of lactobacilli. Furthermore, free PUFA were also demonstrated to alter the adhesion capacity of the intestinal epithelial cells; n-6 PUFA tended to inhibit the Caco-2 adhesion of probiotics, whereas n-3 PUFA had either no or minor effects or even promote the bacterial adhesion (especially Lactobacillus casei Shirota) to PUFA treated Caco-2 cells. The results of this study demonstrate the close and bilateral interactions between dietary PUFA and probiotics. Probiotics were shown to influence the absorption and utilization of dietary PUFA, whereas PUFA were shown to alter the functional properties of both probiotics and mucosal epithelia. These findings suggest that a more thorough understanding of interactions between PUFA and intestinal microbiota is a prerequisite, when the beneficial effects of new functional foods containing probiotics are designed and planned for human intervention studies.

Teollisuuden sivutuotteiden hyödyntäminen ekstruusion raaka-aineena

Ilmaston lämpeneminen ja luonnonvarojen ehtyminen ovat nostaneet ympäristöasiat erittäin ajankohtaisiksi ja kierrättämisen merkitys korostuu entisestään. Tässä diplomityössä on käsitelty teollisuuden jätteiden ja sivutuotteiden kierrättämistä puumuovikomposiitin raaka-aineeksi. Työssä on tutkittu Kaakkois-Suomessa olevia tärkeimpiä teollisuuden sivuainevirtoja puumuovikomposiitin kannalta sekä valmistettu puumuovikomposiittia hyödyntämällä kahta kaatopaikalle päätyvää jätettä. Kaakkois-Suomen teollisuuden jätteitä selvitettäessä löytyi paljon puumuovikomposiitin valmistamiseen soveltuvia jätteitä. Mekaanisen metsäteollisuuden sivutuotteita käytetään yleisesti puumuovikomposiitin valmistamiseen. Muita potentiaaliseksi havaittuja raakaaineita ovat mm. lentotuhka, lasikuitujäte, pakkauskartonki, muovijätteet ja vuorivillan valmistuksessa syntyvät jätteet. Koemateriaaleiksi valittiin puunpoltosta peräisin oleva lentotuhka ja vuorivillan valmistamisessa syntyvä vuorivillapöly. Materiaaleilla korvattiin puuta puumuovikomposiitissa ja valmistetulle komposiitille suoritettiin kokeita mekaanisten ominaisuuksien selvittämiseksi. Molempien materiaalien kohdalla ominaisuuksien havaittiin parantuneen ilman täyteainetta valmistettuun komposiittiin verrattuna.

Teollinen symbioosi - kansallisen ohjelman toteuttaminen Suomessa Britanniaan verrattuna

This master thesis examines the possibility of implementing a national industrial symbiosis programme in Finland. Industrial symbiosis is a close cooperation between companies in which the actors make use of each other's wastes and by-products as raw materials for pro-cesses. Symbiosis programme aims to promote industrial symbiosis by identifying possible synergies. In the United Kingdom (UK), a national level programme NISP (National Industri-al Symbiosis Programme) has been successfully implemented. This thesis studies whether it would be possible to implement a similar program in Finland. The implementation of the pro-gram in Finland is evaluated by analyzing and comparing Finnish and British business envi-ronments using PESTEL and diamond models. The goal is to identify factors that promote or hinder the implementation of the programme in Finland. Based on this study, it can be said that implementing the programme in Finland is possible. The programme can be carried out in almost the same principles as in the UK, but some char-acteristics of the Finnish business environment, such as the high level of technological know-how, should especially be taken as an advantage. On the other hand, there are features, such as low level domestic demand, which may prevent the implementation of the program unless they are given special attention.

New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Paikalliset elinkeinot ja ilmastonmuutos Kaakkois-Suomen alueella

Kasvihuonekaasujen vähentäminen on lähitulevaisuudessa välttämätöntä ilmastonmuutoksen torjunnassa. Tämä tosiasia tulisi nähdä niin yrityksissä kuin kunnissakin mahdollisuutena, johon liittyvillä toimenpiteillä voitaisiin kehittää myös alueen liiketoimintaa ja elinkeinoelämää. Tämän tutkimuksen tavoitteena oli löytää Kaakkois- Suomen kannalta tehokkaimmat keinot ja toimintamallit alueen liiketoiminnan edistämiseksi kasvihuonekaasupäästöjä hillitsevään suuntaan. Työssä on käsitelty erityisesti kunnan toimintaan liittyviä vaikutusmahdollisuuksia tavoitteiden saavuttamisessa. Tutkimus on toteutettu osana Suomen Kuntaliitto Ry:n koordinoimaa kuntienilmastonsuojelukampanjaa. Tutkimus on luonteeltaan kirjallisuuden pohjalta tehty esiselvitys. Työhön sisältyvien esimerkkitapausten osalta on tietoa hankittu myös haastattelemalla alueen yrityksiä. Tutkimuksen alkuvaiheessa on kartoitettu Kaakkois-Suomen alueellisia erityispiirteitä ja potentiaaleja. Työssä on arvioitu esimerkiksi uusiutuvien energialähteiden lisäämispotentiaalien käyttöönottamisella saavutettavat kasvihuonekaasupäästöjen vähenemät sekä työllisyysvaikutukset Kaakkois-Suomen alueella. Potentiaalien luoman pohjan perusteella on selvitetty mahdollisuuksia kehittää alueen elinkeinorakenteeseen soveltuvaa liiketoimintaa. Kasvihuonekaasuja vähentävän liiketoiminnan edistämiseksi on selvitetty keinoja sekä olemassa olevien yritysten kilpailukyvyn parantamiseen että uuden liiketoiminnan kehittämiseen liittyen. Näiden tavoitteiden saavuttamisessa nähtiin yritysten verkostoitumisen olevan eräs tärkeä keino, jolla voidaan parantaa mm. alueen lukuisten pienten yritysten mahdollisuuksia suurten kokonaistoimitusten tuottamisessa. Työssä on esitetty kunnan toimintaan soveltuva toimintamalli yritysten verkostoimiseksi. Jätteiden ja sivutuotteiden osalta työssä on esitetty materiaalivirtojen hyötykäyttöön ohjaamiseen erikoistunutta liiketoimintaa niin sanotun materiaalipörssin muodossa. Myös koulutuksen, tutkimuksen ja rahoituksen tarjontaa kasvihuonekaasuja vähentävän liiketoiminnan kehittämisen tueksi on selvitetty Kaakkois-Suomen alueella. Tutkimuksen sisällössä ovat esimerkkitapaukset keskeisessä asemassa. Niiden puitteissa on haastateltu paikallisen alueen yrityksiä ja viranomaisia. Esimerkkitapauksissa on selvitetty materiaalipörssin, lämpöyrittäjyyden sekä erään yrityksen verkostoimiseen liittyviä tekijöitä ja keinoja. Haastatteluista ja kirjallisuudesta saatuihin tietoihin perustuen on ehdotettu toimintavaihtoehtoja toiminnan kehittämiseksi. Tutkimuksen tulosten perusteella on lopuksi esitetty suunnitelma jatkotoimenpiteistä, joilla tuloksia lähdetään viemään käytännön tasolle.

Recovery of carboxylic acids from aqueous streams by extraction and back extraction

Separation of carboxylic acids from aqueous streams is an important part of their manufacturing process. The aqueous solutions are usually dilute containing less than 10 % acids. Separation by distillation is difficult as the boiling points of acids are only marginally higher than that of water. Because of this distillation is not only difficult but also expensive due to the evaporation of large amounts of water. Carboxylic acids have traditionally been precipitated as calcium salts. The yields of these processes are usually relatively low and the chemical costs high. Especially the decomposition of calcium salts with sulfuric acid produces large amounts of calcium sulfate sludge. Solvent extraction has been studied as an alternative method for recovery of carboxylic acids. Solvent extraction is based on mixing of two immiscible liquids and the transfer of the wanted components form one liquid to another due to equilibrium difference. In the case of carboxylic acids, the acids are transferred from aqueous phase to organic solvent due to physical and chemical interactions. The acids and the extractant form complexes which are soluble in the organic phase. The extraction efficiency is affected by many factors, for instance initial acid concentration, type and concentration of the extractant, pH, temperature and extraction time. In this paper, the effects of initial acid concentration, type of extractant and temperature on extraction efficiency were studied. As carboxylic acids are usually the products of the processes, they are wanted to be recovered. Hence the acids have to be removed from the organic phase after the extraction. The removal of acids from the organic phase also regenerates the extractant which can be then recycled in the process. The regeneration of the extractant was studied by back-extracting i.e. stripping the acids form the organic solution into diluent sodium hydroxide solution. In the solvent regeneration, the regenerability of different extractants and the effect of initial acid concentration and temperature were studied.

Calculation of the carbon footprint of Finnish barley products - methodology and possible applications

The purpose of this thesis was to define how product carbon footprint analysis and its results can be used in company's internal development as well as in customer and interest group guidance, and how these factors are related to corporate social responsibility. From-cradle-to-gate carbon footprint was calculated for three products; Torino Whole grain barley, Torino Pearl barley, and Elovena Barley grit & oat bran, all of them made of Finnish barley. The carbon footprint of the Elovena product was used to determine carbon footprints for industrial kitchen cooked porridge portions. The basic calculation data was collected from several sources. Most of the data originated from Raisio Group's contractual farmers and Raisio Group's cultivation, processing and packaging specialists. Data from national and European literature and database sources was also used. The electricity consumption for porridge portions' carbon footprint calculations was determined with practical measurements. The carbon footprint calculations were conducted according to the ISO 14044 standard, and the PAS 2050 guide was also applied. A consequential functional unit was applied in porridge portions' carbon footprint calculations. Most of the emissions from barley products' life cycle originate from primary production. The nitrous oxide emissions from cultivated soil and the use and production of nitrogenous fertilisers contribute over 50% of products' carbon footprint. Torino Pearl barley has the highest carbon footprint due to the lowest processing output. The reductions in products' carbon footprint can be achieved with developments in cultivation and grain processing. The carbon footprint of porridge portion can be reduced by using domestically produced plant-based ingredients and by making the best possible use of the kettle. Carbon footprint calculation can be used to determine possible improvement points related to corporate environmental responsibility. Several improvement actions are related to economical and social responsibility through better raw material utilization and expense reductions.