Recovery of Hemicelluloses from Wood Hydrolysates by Membrane Filtration

Hemicelluloses are among the most important natural resources that contain polysaccharides. In this study the separation and purification of hemicelluloses from water extraction liquors containing wood hemicelluloses, lignin compounds and monosaccharide by using membrane filtration was investigated. The isolation of the hemicelluloses from the wood hydrolysates was performed in two steps: concentration of high molar mass hemicelluloses by ultrafiltration and separation of low molar mass hemicelluloses from monomeric sugars using tight ultrafiltration membranes. The purification of the retained hemicelluloses was performed by diafiltration. During the filtration experiments, the permeate flux through ultrafiltration and tight ultrafiltration membranes was relatively high. The fouling ability of the used membranes was relatively low. In our experiments, the retention of hemicelluloses using two filtration steps was almost complete. The separation of monosaccharides from hemicelluloses was relatively high and the purification of hemicelluloses by diafiltration was highly efficient. The separation of lignin from hemicelluloses was partially achieved. Diafiltration showed potential to purify retained hemicelluloses from lignin and other organics. The best separation of lignin from hemicelluloses in the first filtration step was obtained using the UC005 membrane. The GE-5 and ETNA01PP membranes showed potential to purify and separate lignin from hemicelluloses. However, the feed solution of the second filtration stages (from different ultrafiltration membranes) affected the permeate flux and the separation of various extracted compounds from hemicelluloses. The GE-5 and ETNA01PP membranes gave the efficient purification of the hemicelluloses when using diafiltration. Separation of degraded xylan from glucomannan (primary spruce hemicelluloses) was also possible using membrane filtration. The best separation was achieved using the GE-5 membrane. The retention of glucomannan was three times higher than xylan retention.

Fractionation of Wood Extracts

The aim of this thesis was to fractionate wood extracts into pure fractions using membrane technology, to observe membrane behaviour in solvents and to study the effect of conditioning on membrane performance. Four different wood extracts were used in the performed filtrations. In the literature part, the focus was on the effect of different solvent properties on polymeric membranes, especially on their retention and flux. Solute properties, such as shape, polarity and charge, were examined. Transport models, membrane stability and ways to improve the stability, when solvents were filtered, were also discussed. The experimental part consisted of a series of filtrations, where the effect of the wood extracts and solvent concentration on solute retention was observed. Polymeric and ceramic membranes were tested under different conditions and the solute analyses were performed with GC and GC-MS. It was discovered that it is possible to fractionate wood extracts using membrane technology to some extent, but more research must be done to understand the mechanisms behind the various interactions between the solvent and the membrane. Conditioning was also considered as an important part of the membrane pre-treatment.

Profiles of Second Language Learners in Bilingual Education: A Comparative Study of the Characteristics of Finnish and American Students

The purpose of this comparative study is to profile second language learners by exploring the factors which have an impact on their learning. The subjects come from two different countries: one group comes from Milwaukee, US, and the other from Turku, Finland. The subjects have attended bilingual classes from elementary school to senior high school in their respective countries. In the United States, the subjects (N = 57) started in one elementary school from where they moved on to two high schools in the district. The Finnish subjects (N = 39) attended the same school from elementary to high school. The longitudinal study was conducted during 1994-2004 and combines both qualitative and quantitative research methods. A Pilot Study carried out in 1990-1991 preceded the two subsequent studies that form the core material of this research. The theoretical part of the study focuses first on language policies in the United States and Finland: special emphasis is given to the history, development and current state of bilingual education, and the factors that have affected policy-making in the provision of language instruction. Current language learning theories and models form the theoretical foundation of the research, and underpin the empirical studies. Cognitively-labeled theories are at the forefront, but sociocultural theory and the ecological approach are also accounted for. The research methods consist of questionnaires, compositions and interviews. A combination of statistical methods as well as content analysis were used in the analysis. The attitude of the bilingual learners toward L1 and L2 was generally positive: the subjects enjoyed learning through two languages and were motivated to learn both. The knowledge of L1 and parental support, along with early literacy in L1, facilitated the learning of L2. This was particularly evident in the American subject group. The American subjects’ L2 learning was affected by the attitudes of the learners to the L1 culture and its speakers. Furthermore, the negative attitudes taken by L1 speakers toward L2 speakers and the lack of opportunities to engage in activities in the L1 culture affected the American subjects’ learning of L2, English. The research showed that many American L2 learners were isolated from the L1 culture and were even afraid to use English in everyday communication situations. In light of the research results, a politically neutral linguistic environment, which the Finnish subjects inhabited, was seen to be more favorable for learning. The Finnish subjects were learning L2, English, in a neutral zone where their own attitudes and motivation dictated their learning. The role of L2 as a means of international communication in Finland, as opposed to a means of exercising linguistic power, provided a neutral atmosphere for learning English. In both the American and Finnish groups, the learning of other languages was facilitated when the learner had a good foundation in their L1, and the learning of L1 and L2 were in balance. Learning was also fostered when the learners drew positive experiences from their surroundings and were provided with opportunities to engage in activities where L2 was used.

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.

Research of wood fuel market in North-West of Russia

The main purposes of this study are analyzing of forest sector of North-West and research of potentials of wood fuel market in this region. Research is focused on definition of the most perspective areas for export of wood fuel: logging residues, industrial wood processing residues, pellets and briquettes. Russian wood energy industry is very young in comparison with European countries. Nowadays there are no support and serious attention from the government to this sector. Hence almost all wood fuel market is oriented to the Western Europe. Export of wood fuel is dominated over the internal consumption. Pellet production in North –West is rapidly growing. Despite internal market has been developed the lion's share of pellets goes to export. Part of industrial wood processing residues is used by producers for their own goals, part goes to the export and rest of them is not used at all. Logging residues as raw materials for fuel have great potentials; most of them are left in a forest. Special techniques for their processing are too expensive for Russian entrepreneur. Some parts of North –West, which are situated close to the border with European countries, are potential for export. Political, economical and logistical challenges are complicated facilities for foreign customer to purchase wood fuel in remote parts of North-West. However some decisions for solving this problem exist and Russian manufactures are still interested in export of their products.

Wood pellet markets in Russia

Bioenergy came to Russia through wood pellets. On account of prevalence of oil and gas in the Russian economy «bioenergy» has come with a great delay. Certainly, there were many woodworking enterprises and even municipal boiler-houses using wood waste and fire wood for energy reception, but this activity was not purposeful. More likely it was connected with necessity of waste recycling and with the organization of heat supply in the remote areas of the country. However, in 2001 was founded the first pellet plant in Russia. The purpose of this work was to analyze wood pellets market in Russia, investigate current situation on the home and export market, evaluates supply and demand development, opportunities for wood pellets manufactures in Russia, the main manufactures in Russian market; cost and prices for wood pellets in Russia. Also the work was intended to give better understanding of the main problems of wood pellets industry in Russia. Besides, this work had updated information about Russian customs and logistic systems.

Molecular Characteristics of Neuroblastoma with Special Reference to Novel Prognostic Factors and Diagnostic Applications

Molecular Characteristics of Neuroblastoma with Special Reference to Novel Prognostic Factors and Diagnostic Applications Department of Medical Biochemistry and Genetics Annales Universitatis Turkuensis, Medica-Odontologica, 2009, Turku, Finland Painosalama Oy, Turku, Finland 2009 Background: Neuroblastoma, which is the most common and extensively studied childhood solid cancer, shows a great clinical and biological heterogeneity. Most of the neuroblastoma patients older than one year have poor prognosis despite intensive therapies. The hallmark of neuroblastoma, biological heterogeneity, has hindered the discovery of prognostic tumour markers. At present, few molecular markers, such as MYCN oncogene status, have been adopted into clinical practice. Aims: The aim of the study was to improve the current prognostic methodology of neuroblastoma, especially by taking cognizance of the biological heterogeneity of neuroblastoma. Furthermore, unravelling novel molecular characteristics which associate with neuroblastoma tumour progression and cell differentiation was an additional objective. Results: A new strictly defined selection of neuroblastoma tumour spots of highest proliferation activity, hotspots, appeared to be representative and reliable in an analysis of MYCN amplification status using a chromogenic in situ hybridization technique (CISH). Based on the hotspot tumour tissue microarray immunohistochemistry and high-resolution oligo-array-based comparative genomic hybridization, which was integrated with gene expression and in silico analysis of existing transcriptomics, a polysialylated neural cell adhesion molecule (NCAM) and poorly characterized amplicon at 12q24.31 were discovered to associate with outcome. In addition, we found that a previously considered new neuroblastoma treatment target, the mutated c-kit receptor, was not mutated in neuroblastoma samples. Conclusions: Our studies indicate polysialylated NCAM and 12q24.31 amplicon to be new molecular markers with important value in prognostic evaluation of neuroblastoma. Moreover, the presented hotspot tumour tissue microarray method together with the CISH technique of the MYCN oncogene copy number is directly applicable to clinical use. Key words: neuroblastoma, polysialic acid, neural cell adhesion molecule, MYCN, c-kit, chromogenic in situ hybridization, hotspot

The effect of microfibrillated cellulose addition on drying shrinkage and dimensional stability of wood-free paper

Microfibrillated cellulose (MFC) is known to enhance strength properties of paper. Improved strength usually means increased bonding which is strongly connected to dimensional instability of paper. Dimensional instability is due to changes in moisture content of paper; when paper is moistened it expands and when dried, it shrinks. Hygroexpansion is linked to end-use problems and excessive drying shrinkage consumes strength potential. Effective use of materials requires controlling of these phenomena. There isn’t yet data concerning dimensional stability of papers containing MFC which restricts wider use of MFC. Main objective of the work was to evaluate dimensional stability of wood-free paper containing different amounts of MFC. Sheets were dried with different methods to see how drying strains effected on drying shrinkage and hygroexpansion. Also tensile strength was measured to find out the effect of MFC. Results were compared to sheets containing kraft fines and in some test points cationic starch was used alongside with MFC. MFC increased the dimensional instability of freely dried sheets. As the amounts of MFC increased the effects on dimensional stability became more severe. However the fineness of MFC didn’t play any important role. Both hygroexpansion and drying shrinkage were decreased with cationic starch addition. Prevention of drying shrinkage over powered the effects of additives on hygroexpansion. Tensile strength improved up till 7 % addition amount which could be set as the upper limit of MFC addition when paper preparation and tensile strength are concerned.

Hemicellulose extracted Kraft pulp as a raw material of paper

The transformation of a traditional pulp mill into an integrated forest biorefinery utilizing wood-derived biomass presents a promising opportunity for enterprise revival of the pulp and paper industry by offering new sources of revenue and significantly improved industry profitability. One proposed next generation process step for an integrated forest biorefinery is the extraction of hemicelluloses, allowing the co-production of pulp and ethanol or chemicals. The extraction of hemicelluloses, however, will likely have downstream effects on pulp quality. In the literature survey an overview of the integrated forest biorefinery and possible next generation technologies implementable in such facility were reviewed. Moreover, some hemicellulose extraction methods suitable for the co-production of pulp and hemicellulose products were looked into in more detail. Also, an overview on the significance of pulp’s hemicellulose content on papermaking properties of pulp fibers was made. In the literature it is stated that the hemicellulose content of pulp affects on many papermaking properties of pulp fibers, hornification and paper strength properties in particular. In the experimental part the goal was to investigate what effects alkaline hemicellulose extraction after bleaching has on the papermaking properties of birch Kraft pulp. It was discovered that tested pulps, normal and hemi-poor birch Kraft pulp, were different in many ways regarding to pulp properties. Differences were observed in both physical and chemical characteristics. Furthermore, clear distinctions were seen in tested paper properties, especially in strength properties, between the handsheets made from hemi-poor or normal birch Kraft pulp. Hemi-poor and normal birch Kraft pulps were also compared as a raw material of laboratory made copy paper. Based on this comparison, usage of hemi-poor birch pulp as the raw material of copy paper does not drastically deteriorate its quality.

Factors affecting the usability of aspen (Populus tremula) wood dried at different temperature levels

In this dissertation the main aim was to study the usability of aspen wood in the mechanical wood processes, especially the factors that affect the usability of aspen wood, which is dried at different temperature levels. The problematic of varying temperatures from level to another seem to have significant effects on distortions. According to the studies conducted, many practical solutions for drying of aspen timber can be made. European aspen sawn timber should be dried in relatively narrow widths, short lengths, edged and sawn pith free. The results achieved give an interesting view for the distortions of aspen wood between HT drying and heat treatment. The most significant result is that cupping seems to decrease when increasing temperature level from HT drying to heat treatment phase. The difference is significant. Other very obvious result is that bow and crook are increasing between these two temperature levels, bow significantly. Also the modelling gives a good background for this result since cupping is reduced by higher temperatures. It can also be assumed that these distortions can be affected for example by sorting out the timber used to different moisture levels before drying. This could be a very simple solution for practical purposes. From practical point of view, it was also noted during the drying tests performed that the discoloration seem to be no problem for aspen boards dried in temperatures under 150 °C. Altogether, this dissertation covers many interesting points of view of factors affecting distortions of wood in different temperature stages. Aspen as species in use of mechanical wood industries seems to be a species suitable for component production. According to the results, the best yield from aspen timber can be achieved in industry that can utilize relatively short components of sawn wood. Results achieved give a significant indication about the factors affecting distortions of wood at different temperature stages of drying, especially considering European aspen.

Effects of Surface Properties and Wood Modification into Direct Printing on Wood

Building industry is a high volume branch which could provide prominent markets for wood based interior decoration solutions. Competition in interior decoration markets requires versatility in appearance. Versatility in wood appearance and added value could be achieved by printing grain patterns of different species or images directly onto wood. The problem when planning wood printing’s implementing into durable applications is basically how to transfer a high quality image or print sustainably onto wood, which is porous, heterogeneous, dimensionally unstable, non-white and rough. Wood preservation or treating, and modification can provide durability against degradation but also effect to the surface properties of wood which will effect on printability. Optimal adhesion is essential into print quality, as too high ink absorbance can cause spreading and too low ink absorbance cause pale prints. Different printing techniques have different requirements on materials and production. The direct printing on wood means, that intermedias are not used. Printing techniques with flexible printing plates or in fact non-impact techniques provide the best basis for wood printing. Inkjet printing of wood with different mechanical or chemical surface treatments, and wood plastic composite material gave good results that encourage further studies of the subject. Sanding the wood surface anti-parallel to the grain gave the best overall printing quality. Spreading parallel to the grain could not be avoided totally, except in cases where wood was treated hydrophobic so adhesion of the ink was not sufficient. Grain pattern of the underlying wood stays clearly visible in the printed images. Further studies should be made to fine tune the methods that already gave good results. Also effects of moisture content of wood, different inks, and long-term exposure to UV-radiation should be tested.

The influence of crystallization conditions on the filtration characteristics of sulphathiazole suspensions

Cooling crystallization is one of the most important purification and separation techniques in the chemical and pharmaceutical industry. The product of the cooling crystallization process is always a suspension that contains both the mother liquor and the product crystals, and therefore the first process step following crystallization is usually solid-liquid separation. The properties of the produced crystals, such as their size and shape, can be affected by modifying the conditions during the crystallization process. The filtration characteristics of solid/liquid suspensions, on the other hand, are strongly influenced by the particle properties, as well as the properties of the liquid phase. It is thus obvious that the effect of the changes made to the crystallization parameters can also be seen in the course of the filtration process. Although the relationship between crystallization and filtration is widely recognized, the number of publications where these unit operations have been considered in the same context seems to be surprisingly small. This thesis explores the influence of different crystallization parameters in an unseeded batch cooling crystallization process on the external appearance of the product crystals and on the pressure filtration characteristics of the obtained product suspensions. Crystallization experiments are performed by crystallizing sulphathiazole (C9H9N3O2S2), which is a wellknown antibiotic agent, from different mixtures of water and n-propanol in an unseeded batch crystallizer. The different crystallization parameters that are studied are the composition of the solvent, the cooling rate during the crystallization experiments carried out by using a constant cooling rate throughout the whole batch, the cooling profile, as well as the mixing intensity during the batch. The obtained crystals are characterized by using an automated image analyzer and the crystals are separated from the solvent through constant pressure batch filtration experiments. Separation characteristics of the suspensions are described by means of average specific cake resistance and average filter cake porosity, and the compressibilities of the cakes are also determined. The results show that fairly large differences can be observed between the size and shape of the crystals, and it is also shown experimentally that the changes in the crystal size and shape have a direct impact on the pressure filtration characteristics of the crystal suspensions. The experimental results are utilized to create a procedure that can be used for estimating the filtration characteristics of solid-liquid suspensions according to the particle size and shape data obtained by image analysis. Multilinear partial least squares regression (N-PLS) models are created between the filtration parameters and the particle size and shape data, and the results presented in this thesis show that relatively obvious correlations can be detected with the obtained models.