Fractionation of wood hydrolysate by ultrafiltration membranes at high temperature

Ultrafiltration (UF) is already used in pulp and paper industry and its demand is growing because of the required reduction of raw water intake and the separation of useful compounds from process waters. In the pulp and paper industry membranes might be exposed to extreme conditions and, therefore, it is important that the membrane can withstand them. In this study, extractives, hemicelluloses and lignin type compounds were separated from wood hydrolysate in order to be able to utilise the hemicelluloses in the production of biofuel. The performance of different polymeric membranes at different temperatures was studied. Samples were analysed for total organic compounds (TOC), lignin compounds (UV absorption at 280 nm) and sugar. Turbidity, conductivity and pH were also measured. The degree of fouling of the membranes was monitored by measuring the pure water flux before and comparing it with the pure water flux after the filtration of hydrolysate. According to the results, the retention of turbidity was observed to be higher at lower temperature compared to when the filtrations were operated at high temperature (70 °C). Permeate flux increased with elevated process temperature. There was no detrimental effect of temperature on most of the membranes used. Microdyn-Nadir regenerated cellulose membranes (RC) and GE-Osmonics thin film membranes seemed to be applicable in the chosen process conditions. The Polyethersulphone (NF-PES-10 and UH004P) and polysulphone (MPS-36) membranes used were highly fouled, but they showed high retentions for different compounds.

Kuusiviilun esikuivaus puristamalla

Tutkimuksen lähtökohtana oli selvittää, voidaanko viilun valmistusprosessiin liittää uusi työvaihe, viilun esikuivaus. Esikuivauksen tarkoituksena on poistaa kosteutta viiluista ennen varsinaista kuivausta ja lisätä näin kuivauskapasiteettia. Tehdyissä tutkimuksissa viilut esikuivattiin nipuissa puristamalla. Muuttujina esikuivauksessa toimivat puristusaika ja -paine. Niiden määrittelyn lähtökohtana pidettiin sitä, etteivät viilun ominaisuudet saa merkittävästi heikentyä esikuivauksen aikana ja samalla viiluista on saatava mahdollisimman paljon kosteutta pois. Aikaisempien tutkimusten avulla selvitettiin vanerin valmistuksen, viilun kuivauksen sekä viilun esikuivauksen teoriaa. Lisäksi selvitettiin puun ominaisuuksien antamia mahdollisuuksia ja rajoitteita esikuivaukseen liittyen. Tutkimus koostui kahdesta osasta: laboratorio- ja tehdastutkimuksista. Laboratoriotutkimuksen tarkoituksena oli toimia tehdastutkimuksen esitutkimuksena. Laboratoriotutkimuksessa tutkittiin ainoastaan esikuivauksen vaikutusta märille viiluille. Tehdastutkimusosiossa esikuivatuista viiluista valmistettiin normaalin vanerinvalmistusprosessin kautta levyjä, joiden ominaisuuksia verrattiin normaaleista viiluista valmistettuihin vanereihin. Viilujen esikuivauksen todettiin pienentävän kuusiviilujen kosteuspitoisuutta. Tämän lisäksi kosteuspitoisuuden muutokset esikuivauksen aikana tapahtuivat tasaisesti niin yksittäisen viilun kuin viilunipunkin sisällä. Esikuivatuista viiluista valmistetut vanerilevyt täyttivät kaikki standardien sekä vanerin laadunvalvontasopimuksen asettamat vaatimukset. Esikuivauksen haitaksi tutkimuksissa todettiin viilun paksuuden pienentymä. Ennen esikuivauksen soveltamista teolliseen käyttöön nähtiin tarvetta lisätutkimukselle, jossa tulisi selvittää suurempien viilunippukokojen esikuivaamista sekä niiden varsinaista kuivaamista heti esikuivauksen jälkeen.

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.

Bioenergiaa ja ravinteita kasvi- ja eläinperäisistä sivuainevirroista Parikkalassa

Euroopan unionissa pyritään lisäämään uusiutuvien energialähteiden käyttöä. Tämän työn tavoitteena oli selvittää Parikkalan kunnan alueella muodostuvat biomassat sekä tutkia niiden hyötykäyttömahdollisuuksia sähkön, lämmön sekä lannoitteiden tuotannossa. Käsiteltäviä biomassoja ovat eläintilojen lietteet ja lannat, biojätteet ja yhdyskuntalietteet, vesistöjen kunnostuksessa syntyvät biomassat sekä peltobiomassat ja metsäbiomassa. Mädätyksen kannalta olennaisinta on materiaalien kosteus ja haihtuvan orgaanisen aineksen pitoisuus sekä siitä saatava biokaasumäärä. Poltossa polttoaineen kuiva-aineen lämpöarvo ja kosteus määrittelevät saadun hyödyn. Kompostoinnissa on tärkeää huolehtia riittävästä ilman saannista ja riittävästä viipymäajasta. Hyödynnettäessä biokaasua sähkön ja lämmön yhteistuotannossa on tärkeää löytää hyötykäyttö myös muodostuvalle lämmölle. Poltosta saatavan tuhkan hyötykäyttö onnistuu metsälannoitteena, kun poltetaan turvetta tai puuta. Kompostia voidaan hyödyntää maanparannusaineena. Parikkalan alueella tarkasteltiin biomassojen nykyistä ja mahdollista tulevaa hyötykäyttöä. Tarkastelu tehtiin skenaarioiden avulla. Skenaarioihin kuuluvat mädätyksen ja polton maksimipotentiaalit sekä keskitetyn ja hajautetun käsittelyn skenaariot. Alueelta on saatavissa paljon biomassoja, joista massaltaan suurin on eläintilojen lannat. Alueella on hankaluutena löytää sopiva kulutuskohde biokaasusta tuotetulle lämmölle, mutta sopivana kohteena voisi toimia alueella oleva suuri sikala tai lämpökeskukset.

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.

Building wood debris piles benefits avian seed dispersers in burned and logged Mediterranean pine forests

Salvage logging is a common practice carried out in burned forests worldwide, and intended to mitigate the economic losses caused by wildfires. Logging implies an additional disturbance occurring shortly after fire, although its ecological effects can be somewhat mitigated by leaving wood debris on site. The composition of the bird community and its capacity to provide ecosystem services such as seed dispersal offleshy-fruited plants have been shown to be affected by postfire logging. We assessedthe effects of the habitat structure resulting from different postfire management practices on the bird community, in three burned pine forests in Catalonia (western Mediterranean). For this purpose, we focused on the group of species that is responsible for seed dispersal, a process which takes place primarily during the winter in theMediterranean basin. In addition, we assessed microhabitat selection by seed disperser birds in such environments in relation to management practices. Our results showed a significant, positive relationship between the density of wood debris piles and the abundance of seed disperser birds. Furthermore, such piles were the preferredmicrohabitat of these species. This reveals an important effect of forest management on seed disperser birds, which is likely to affect the dynamics of bird-dependent seed dispersal. Thus, building wood debris piles can be a useful practice for the conservation of both the species and their ecosystem services, while also being compatible with timber harvesting

A convenient method for the determination of moisture in aromatic plants

A method is proposed for the determination of the moisture content of aromatic plants. This method is based on the co-distillation of the starting material in a modified Clevenger apparatus with four organic solvents (toluene, cyclohexane, dichloromethane and carbon tetrachloride). The results were compared with those obtained by oven drying at 105 ºC and steam distillation of the essential oil. The efficiencies of the methods were shown to be equivalent. The solvent distillation method was more practical, especially with respect to operating time (2 h).

Does soil moisture overrule temperature dependence of soil respiration in Mediterranean riparian forests?

Soil respiration (SR) is a major component of ecosystems' carbon cycles and represents the second largest CO2 flux in the terrestrial biosphere. Soil temperature is considered to be the primary abiotic control on SR, whereas soil moisture is the secondary control factor. However, soil moisture can become the dominant control on SR in very wet or dry conditions. Determining the trigger that makes soil moisture as the primary control factor of SR will provide a deeper understanding on how SR changes under the projected future increase in droughts. Specific objectives of this study were (1) to investigate the seasonal variations and the relationship between SR and both soil temperature and moisture in a Mediterranean riparian forest along a groundwater level gradient; (2) to determine soil moisture thresholds at which SR is controlled by soil moisture rather than by temperature; (3) to compare SR responses under different tree species present in a Mediterranean riparian forest (Alnus glutinosa, Populus nigra and Fraxinus excelsior). Results showed that the heterotrophic soil respiration rate, groundwater level and 30 cm integral soil moisture (SM30) decreased significantly from the riverside moving uphill and showed a pronounced seasonality. SR rates showed significant differences between tree species, with higher SR for P. nigra and lower SR for A. glutinosa. The lower threshold of soil moisture was 20 and 17% for heterotrophic and total SR, respectively. Daily mean SR rate was positively correlated with soil temperature when soil moisture exceeded the threshold, with Q10 values ranging from 1.19 to 2.14; nevertheless, SR became decoupled from soil temperature when soil moisture dropped below these thresholds.

Determination of moisture content and water activity in algae and fish by thermoanalytical techniques

The water content in seafoods is very important since it affects their sensorial quality, microbiological stability, physical characteristics and shelf life. In this study, thermoanalytical techniques were employed to develop a simple and accurate method to determine water content (moisture) by thermogravimetry (TG) and water activity from moisture content values and freezing point depression using differential scanning calorimetry (DSC). The precision of the results suggests that TG is a suitable technique to determine moisture content in biological samples. The average water content values for fish samples of Lutjanus synagris and Ocyurus chrysurus species were 76.4 ± 5.7% and 63.3 ± 3.9%, respectively, while that of Ulva lactuca marine algae species was 76.0 ± 4.4%. The method presented here was also successfully applied to determine water activity in two species of fish and six species of marine algae collected in the Atlantic coastal waters of Bahia, in Brazil. Water activity determined in fish samples ranged from 0.946 - 0.960 and was consistent with values reported in the literature, i.e., 0.9 - 1.0. The water activity values determined in marine algae samples lay within the interval of 0.974 - 0.979.

Moisture sorption isotherms and isosteric heat determination in Chilean papaya (Vasconcellea pubescens)

The moisture sorption isotherms of Chilean papaya were determined at 5, 20, and 45 ºC, over a relative humidity range of 10-95%. The GAB, BET, Oswin, Halsey, Henderson, Smith, Caurie and Iglesias-Chirife models were applied to the sorption experimental data. The goodness of fit of the mathematical models was statistically evaluated by means of the determination coefficient, mean relative percentage deviation, sum square error, root-mean-square error, and chi-square values. The GAB, Oswin and Halsey models were found to be the most suitable for the description of the sorption data. The sorption heats calculated using the Clausius-Clapeyron equation were 57.35 and 59.98 kJ·mol-1, for adsorption and desorption isotherms, respectively.

Constituintes químicos do caule de Senna reticulata Willd. (Leguminoseae): Chemical constituents isolated from the wood of Senna reticulata Willd.

The phytochemical investigation of the wood extracts of Senna reticulata (Leguminoseae) yielded six anthraquinones: chrysophanol, physcion, aloe-emodin, 1,3,8-trihydroxyanthraquinone, 3-methoxy-1,6,8-trihydroxyanthraquinone, emodin and the chrysophanol-10,10' bianthrone. The triterpenes a and b-amirin, the steroids b-sitosterol and stigmasterol as well as the flavonoid kaempferol were also identified. The structures were established by spectral analysis, including two-dimensional NMR techniques. It is the first report of 1,3,8-trihydroxyanthraquinone and 3-methoxy-1,6,8-trihydroxyanthraquinone in higher plants.

Chemical constituents of the wood from Zanthoxylum quinduense Tul. (Rutaceae)

Phytochemical investigation of the wood from Zanthoxylum quinduense Tul. allowed the isolation and identification of norchelerythrine, decarine, 6-acetonyldihydrochelerythrine, syringaresinol, evofilin C, p-hydroxybenzaldehyde, vanillic acid, a mixture of β-sitosterol, stigmasterol and campesterol and a mixture of saturated and unsaturated fatty acids, and their esters derivatives. The structures of the isolated compounds were elucidated by spectroscopic techniques and comparison with literature data and the mixture of sterols and fatty acids were identified by GC/MS. The antifungal activity of the ethanolic extract, fractions and pure compounds against Fusarium oxysporum f. sp. lycopersici was determined by bioautography. Evofilin C and nochelerytrine were the only substances that present antifungal activity.