Combustion properties of biomass residues rich in phosphorus

Tillgången på traditionella biobränslen är begränsad och därför behöver man ta fram nya, tidigare outnyttjade biobränslen för att möta de uppställda CO2 emissionsmålen av EU och det ständigt ökande energibehovet. Under de senare åren har intresset riktats mot termisk energiutvinning ur olika restfraktioner och avfall. Vid produktion av fordonsbränsle ur biomassa är den fasta restprodukten ofta den största procesströmmen i produktionsanläggningen. En riktig hantering av restprodukterna skulle göra produktionen mera lönsam och mer ekologiskt hållbar. Ett alternativ är att genom förbränning producera elektricitet och/eller värme eftersom dessa restprodukter anses som CO2-neutrala. Målsättningen med den här avhandlingen var att studera förbränningsegenskaperna hos några fasta restprodukter som uppstår vid framställning av förnybara fordonsbränslen. De fyra undersökta materialen är rapskaka, palmkärnskaka, torkad drank och stabiliserat rötslam. I studien används ett stort urval av undersökningsmetoder, från laboratorieskala till fullskalig förbränning, för att identifiera de huvudsakliga utmaningarna förknippade med förbränning av restprodukterna i pannor med fluidiserad bäddteknik. Med hjälp av detaljerad bränslekarakterisering kunde restprodukterna konstateras vara en värdefull källa för värme- och elproduktion. Den kemiska sammansättningen av restprodukterna varierar stort jämfört med mera traditionellt använda biobränslen. En gemensam faktor för alla de studerade restprodukterna är en hög fosforhalt. På grund av de låga fosforkoncentrationerna i de traditionella biobränslena har grundämnet hittills inte ansetts spela någon större roll i askkemin. Experimenten visade nu att fosfor inte mera kan försummas då man studerar kemin i förbränningsprocesser, då allt flera fosforrika bränslen tränger in på energimarknaden.

Steroidien selektiivinen erottaminen sähköavusteisesti mikroemulsioita käyttäen

Mikroemulsiosähkökineettinen kromatografia on sähköavusteinen erotusmenetelmä. Yhdisteiden erottuminen tapahtuu mikroemulsiopisaroiden vaikutuksesta, kun nanometrien kokoiset öljypisarat ovat dispergoituneena veteen valmistettuun puskuriliuokseen. Yleensä mikroemulsiot valmistetaan raakaöljynkin sisältämistä hiilivedyistä, joita ovat esimerkiksi oktaani ja heptaani. Työn kokeellisessa osassa perehdyttiin seitsemän hydrofobisen ja varauksettoman steroidihormonin erottamiseen mikroemulsioliuoksessa kapillaarielektroforeesitekniikalla. Työssä valmistettiin öljyistä koostuvia mikroemulsioita, joista osan koostumus valittiin kirjallisuuden perusteella. Työssä kokeiltiin myös uusia mikroemulsiokoostumuksia, joissa käytettiin luonnosta peräisin olevia öljyjä: rypsi-, oliivi-, pellavansiemen- ja saksanpähkinäöljyä. Seitsemästä steroidihormonista viisi yhdistettä saatiin erottumaan optimoiduilla menetelmillä. Steroidien erotus perustuu niiden oktanoli-vesi jakautumiskertoimien avulla saatavaan migraatiojärjestykseen. Mikroemulsiossa, jossa käytettiin 1-oktanolia, steroidihormonit erottuivat nopeammin, kuin saksanpähkinäöljyä käytettäessä. Lyhyimmät migraatioajat saatiin mikroemulsiolla, jossa öljyfaasina käytettiin 1-heksanolia ja viidentenä yhdisteenä asetonitriiliä. Selektiivisimmillään menetelmä on, kun erotus tapahtuu liuoksessa, joka koostuu etyyliasetaatista, natriumdodekyylisulfaatista, butanolista, asetonitriilistä ja natriumtetraboraatista. Toteamisrajat tutkituille steroidihormoneille olivat 0,20–0,43 mg/L mikroemulsioissa.

Greenhouse gas emissions from peat and biomass-derived fuels, electricity and heat — Estimation of various production chains by using LCA methodology

More discussion is required on how and which types of biomass should be used to achieve a significant reduction in the carbon load released into the atmosphere in the short term. The energy sector is one of the largest greenhouse gas (GHG) emitters and thus its role in climate change mitigation is important. Replacing fossil fuels with biomass has been a simple way to reduce carbon emissions because the carbon bonded to biomass is considered as carbon neutral. With this in mind, this thesis has the following objectives: (1) to study the significance of the different GHG emission sources related to energy production from peat and biomass, (2) to explore opportunities to develop more climate friendly biomass energy options and (3) to discuss the importance of biogenic emissions of biomass systems. The discussion on biogenic carbon and other GHG emissions comprises four case studies of which two consider peat utilization, one forest biomass and one cultivated biomasses. Various different biomass types (peat, pine logs and forest residues, palm oil, rapeseed oil and jatropha oil) are used as examples to demonstrate the importance of biogenic carbon to life cycle GHG emissions. The biogenic carbon emissions of biomass are defined as the difference in the carbon stock between the utilization and the non-utilization scenarios of biomass. Forestry-drained peatlands were studied by using the high emission values of the peatland types in question to discuss the emission reduction potential of the peatlands. The results are presented in terms of global warming potential (GWP) values. Based on the results, the climate impact of the peat production can be reduced by selecting high-emission-level peatlands for peat production. The comparison of the two different types of forest biomass in integrated ethanol production in pulp mill shows that the type of forest biomass impacts the biogenic carbon emissions of biofuel production. The assessment of cultivated biomasses demonstrates that several selections made in the production chain significantly affect the GHG emissions of biofuels. The emissions caused by biofuel can exceed the emissions from fossil-based fuels in the short term if biomass is in part consumed in the process itself and does not end up in the final product. Including biogenic carbon and other land use carbon emissions into the carbon footprint calculations of biofuel reveals the importance of the time frame and of the efficiency of biomass carbon content utilization. As regards the climate impact of biomass energy use, the net impact on carbon stocks (in organic matter of soils and biomass), compared to the impact of the replaced energy source, is the key issue. Promoting renewable biomass regardless of biogenic GHG emissions can increase GHG emissions in the short term and also possibly in the long term.

Weeds occurrence in areas submitted to distinct winter crops

In the Western Region of Brazil, it is usual to have two agricultural harvests in the same cropping season. Usually the first crop is soybean, followed by corn. In areas where corn is not planted due to a delayed harvest of soybean, farmers generally do not use winter crops. For these areas, the planting of winter oilseed crops aiming at the production of bio-fuels is one of the best alternatives; in addition, this would help in reducing the occurrence of weed species at the following summer crop. This study aimed to assessing the weed community in distinct winter crops post soybean crop, in terms of species composition, level of infestation and severity of occurrence. The following treatments were evaluated: agriculture under a no-till system with winter fallow, winter oilseed crops (crambe, radish, rapeseed) with no-till agriculture in the summer, and agriculture under a conventional tillage system with winter fallow. Phytosociological evaluations of all treatments were carried out 75 DAE of the oilseed crops, and the diversity indexes of Margalef, Menhinick, Simpson, and Shannon-Weiner were determined. Areas were also grouped by cluster analysis based on UPGMA applied at Jaccard's similarity matrix. Among the treatments with winter coverage, radish was the most efficient crop in suppressing the occurrence of weed species. The area with conventional tillage agriculture and winter fallow allowed for a higher occurrence of troublesome weeds. On the other hand, the area under fallow showed the highest absolute level of infestation. Overall, oilseed crops in the winter contribute to lower levels of infestation by weed species in these areas.

Infestation of weed species in pre-planting of soybean in succession to winter crops

This study aimed to evaluate different crops and plant species planted after soybeans for one year, in terms of their potential to inhibit the occurrence of weed species. The following crops that were planted as second crop after soybeans were evaluated: (1) corn (Zea mays) planted at spacing of 90 cm between rows, intercropped with Brachiaria ruziziensis in the inter-rows; (2) sunflower (Helianthus annuus); (3) crambe (Crambe abyssinica); (4) radish (Raphanus sativus); (5) rapeseed (Brassica napus); and (6) winter fallow - no plantation after soybeans. Phytosociological characterization of weed species was carried out at the pre-planting of soybeans in the following cropping season. Estimations of relative abundance, relative frequence, relative dominance and Importance Value Index were made for each species present. Areas were also intra-characterized by the diversity coefficients of Simpson and modified Shannon-Weiner, and areas were compared using the Jaccard similarity coefficient for presence-only, by multivariate cluster analysis. In the short‑term (a single cropping season), cultivation of winter crops do contribute for lower occurrence of weed species at the pre-planting of soybeans on the subsequent cropping season. The suppressive effects depend both on the species grown in the winter and in the amount of straw left on the soil by these winter crops. Radish was more efficient in inhibiting the occurrence of weed species and rapeseed showed composition of infestation similar to that observed at the area under fallow.

Storage stability of snacks with reduced saturated and trans fatty acids contents

Partially hydrogenated vegetable oil has been used in snack flavoring for its ability to entrap hydrophobic aroma compounds. However, increasing concerns about the health risks of saturated and trans fatty acids (TFA) consumption led to the development of alternative agents for this use. We studied the use of rapeseed oil (O) as a replacement for partially hydrogenated vegetable oil (F) in snack flavoring. Products with several different rapeseed oil contents were designed, packed, and then stored for twenty weeks at room temperature. Fatty acids compositions, TBA reactive substances (TBARS), shear strength and sensory acceptability were assessed throughout storage time. Total replacement reduced saturated fat by 72.5% in relation to market available snacks. TFA were initially absent in these products, but their production occurred spontaneously on the 8th week with gradual increase during storage up to levels still lower than those observed in commercially available snacks. Low TBARS levels and stability of shear strength during the twenty-week of storage were also observed. Snacks flavored with F or O were equally well accepted during the storage period. It is feasible to develop a storage stable snack with reduced saturated and trans fatty acid contents while maintaining the high sensory acceptability typical of this food product.

Preparation and Investigation of Bio-coal Mixture Fuels Used in Large Diesel Engines

Coal slurry was of vital interest during the last century due to its potential as an alternative fuel where liquid fuels were necessary. Recently, environmental impacts of the traditional fuels, similarities of bio-coal to that of coal, and huge bio-coal supply has attracted the attention to prepare bio-coal slurries as a new fuel. Rudolf Diesel who invented the diesel engine on 1895 was of the opinion that diesel engines are capable to use different kinds of fuels due to the special design. He tried some kind of vegetable oil to operate on his IC engine. Recently, due to high energy density and more environmentally friendly fuel, researchers believe that bio-coal slurries could act as a new alternative fuel in large diesel engines. Loads of research on different kinds of bio-coal slurry were done by the other researchers worldwide and a lot of progress to boost slurry’s quality were achieved recently. The present study aims to achieve the ideal condition of different factors affecting on the quality of bio-coal slurry. One charcoal sample and two kinds of torrefied wood were used to investigate and compare the reaction of various factors. The results show a great gap between the quality of slurries made of different samples and more researches are necessary to fully understand the impact of the different parameter and improving the quality.

Evaluación de la biomasa como recurso energético renovable en Cataluña

El objetivo principal es la evaluación de la biomasa como recurso energético renovable en Cataluña. Su alcance requiere el estudio de diversas temáticas, desarrolladas en los doce capítulos que componen el documento.El Capítulo 1 describe los objetivos de la tesis. El Capítulo 2 describe los motivos que justifican la valorización energética del recurso biomasa. El Capítulo 3 presenta la metodología general utilizada. El Capítulo 4 realiza un análisis multicriterio del aprovechamiento energético de biomasa forestal. El Capítulo 5 cuantifica la biomasa disponible para usos energéticos en Cataluña. Los Capítulos 6, 7, 8 y 9 analizan las tecnologías y la viabilidad de la producción de energía con colza y chopo. El Capítulo 10 caracteriza físico-químicamente la biomasa de colza como combustible complementario al actual uso del grano para biodiesel. El Capítulo 11 evalua el uso de cultivos para la producción de productos químicos. El Capítulo 12 resume las Conclusiones generales.

Use of airborne remote sensing to detect riverside Brassica rapa to aid in risk assessment of transgenic crops

High resolution descriptions of plant distribution have utility for many ecological applications but are especially useful for predictive modelling of gene flow from transgenic crops. Difficulty lies in the extrapolation errors that occur when limited ground survey data are scaled up to the landscape or national level. This problem is epitomized by the wide confidence limits generated in a previous attempt to describe the national abundance of riverside Brassica rapa (a wild relative of cultivated rapeseed) across the United Kingdom. Here, we assess the value of airborne remote sensing to locate B. rapa over large areas and so reduce the need for extrapolation. We describe results from flights over the river Nene in England acquired using Airborne Thematic Mapper (ATM) and Compact Airborne Spectrographic Imager (CASI) imagery, together with ground truth data. It proved possible to detect 97% of flowering B. rapa on the basis of spectral profiles. This included all stands of plants that occupied >2m square (>5 plants), which were detected using single-pixel classification. It also included very small populations (<5 flowering plants, 1-2m square) that generated mixed pixels, which were detected using spectral unmixing. The high detection accuracy for flowering B. rapa was coupled with a rather large false positive rate (43%). The latter could be reduced by using the image detections to target fieldwork to confirm species identity, or by acquiring additional remote sensing data such as laser altimetry or multitemporal imagery.

Hybridization between Brassica napus and B. rapa on a national scale in the United Kingdom

Measures blocking hybridization would prevent or reduce biotic or environmental change caused by gene flow from genetically modified (GM) crops to wild relatives. The efficacy of any such measure depends on hybrid numbers within the legislative region over the life-span of the GM cultivar. We present a national assessment of hybridization between rapeseed (Brassica napus) and B. rapa from a combination of sources, including population surveys, remote sensing, pollen dispersal profiles, herbarium data, local Floras, and other floristic databases. Across the United Kingdom, we estimate that 32,000 hybrids form annually in waterside B. rapa populations, whereas the less abundant weedy populations contain 17,000 hybrids. These findings set targets for strategies to eliminate hybridization and represent the first step toward quantitative risk assessment on a national scale.

Use of airborne remote sensing to detect riverside Brassica rapa to aid in risk assessment of transgenic crops

High resolution descriptions of plant distribution have utility for many ecological applications but are especially useful for predictive modeling of gene flow from transgenic crops. Difficulty lies in the extrapolation errors that occur when limited ground survey data are scaled up to the landscape or national level. This problem is epitomized by the wide confidence limits generated in a previous attempt to describe the national abundance of riverside Brassica rapa (a wild relative of cultivated rapeseed) across the United Kingdom. Here, we assess the value of airborne remote sensing to locate B. rapa over large areas and so reduce the need for extrapolation. We describe results from flights over the river Nene in England acquired using Airborne Thematic Mapper (ATM) and Compact Airborne Spectrographic Imager (CASI) imagery, together with ground truth data. It proved possible to detect 97% of flowering B. rapa on the basis of spectral profiles. This included all stands of plants that occupied >2m square (>5 plants), which were detected using single-pixel classification. It also included very small populations (<5 flowering plants, 1-2m square) that generated mixed pixels, which were detected using spectral unmixing. The high detection accuracy for flowering B. rapa was coupled with a rather large false positive rate (43%). The latter could be reduced by using the image detections to target fieldwork to confirm species identity, or by acquiring additional remote sensing data such as laser altimetry or multitemporal imagery.

Assembling spatially explicit landscape models of pollen and spore dispersal by wind for risk assessment

Models of windblown pollen or spore movement are required to predict gene flow from genetically modified (GM) crops and the spread of fungal diseases. We suggest a simple form for a function describing the distance moved by a pollen grain or fungal spore, for use in generic models of dispersal. The function has power-law behaviour over sub-continental distances. We show that air-borne dispersal of rapeseed pollen in two experiments was inconsistent with an exponential model, but was fitted by power-law models, implying a large contribution from distant fields to the catches observed. After allowance for this 'background' by applying Fourier transforms to deconvolve the mixture of distant and local sources, the data were best fit by power-laws with exponents between 1.5 and 2. We also demonstrate that for a simple model of area sources, the median dispersal distance is a function of field radius and that measurement from the source edge can be misleading. Using an inverse-square dispersal distribution deduced from the experimental data and the distribution of rapeseed fields deduced by remote sensing, we successfully predict observed rapeseed pollen density in the city centres of Derby and Leicester (UK).

Effects of variation in the palm stearin: palm olein ratio on the crystallisation of a low-trans shortening

Changes in the theological properties during crystallisation and in the crystal size and morphology of blends containing rapeseed oil with varying percentages of palm stearin (POs) and palm olein (POf) have been studied. The crystals formed from all three blends were studied by confocal laser scanning microscopy, light microscopy and environmental scanning electron microscopy, which revealed the development of clusters of 3-5 individual elementary "spherulites" in the early stages of crystallisation. The saturated triacylglycerol content of the solid crystals separated at the onset of crystallisation was much greater than that in the total fat. Fat blends with a higher content of palm stearin had a more rapid nucleation rate when observed by light microscopy, and this caused an earlier change in the rheological properties of the fat during crystallisation. Using a low torque amplitude (0.005 Pa, which was within the linear viscoelastic region of all samples studied) and a frequency of 1 Hz, the viscoelastic properties of melted fat during cooling were studied. All samples, prior to crystallisation, showed weak viscoelastic liquid behaviour (G '', loss modulus >G', storage modulus). After crystallisation a more "solid like" behaviour was observed (G' similar to or greater than G ''). The blend having the highest concentration of POs was found to have the earliest onset of crystallisation (27% w/w POs; 12 mins, 22% w/w POs; 13.5 mins, 17% w/w POs, 15 mins, respectively). However, there were no significant differences in the time to the point when G' became greater than G' among the three blends. (c) 2006 Elsevier Ltd. All rights reserved.

Effects of composition on fat rheology and crystallisation

The crystallisation behaviour of three fat blends, comprising a commercial shortening, a blend of fats with a very low trans fatty acid content ("low-trans") and a blend including hardened rapeseed oil with a relatively high trans fatty acid content ("high-trans") was studied. Molten fats were lowered to a temperature of 31 degrees C and stirred for 0, 15, 30, 45 and 60 min. Samples were removed and their rheological properties studied, using a controlled stress rheometer, employing a frequency sweep procedure. Effects of the progressive crystallisation at 31 degrees C on the melting profile of fat samples removed from the stirred vessel and solidified at -20 degrees C were also studied by differential scanning calorimetry (DSC). The rheological profiles obtained suggested that all of the fats studied had weak viscoelastic "liquid" structures when melted, but these changed to structures perceived by the rheometer as weak viscoelastic "gels" in the early stages of crystallisation (G' (storage modulus) > G" (loss modulus) over most of the measured frequency range). These subsequently developed into weak viscoelastic semi-solids, showing frequency dependent behaviour on further crystallisation. These changes in behaviour were interpreted as changes from a small number of larger crystals "cross-linking" in a liquid matrix to a larger number of smaller crystals packed with a "slip plane" of liquid oil between them. The rate of crystallisation of the three fats was in the order high trans > low-trans > commercial shortening. Changes in the DSC melting profile due to fractionation of triacylglycerols during the crystallisation at 31 degrees C were evident for all three fats. (c) 2006 Elsevier Ltd. All rights reserved.

Relationship between condensed tannin structures and their ability to precipitate feed proteins in the rumen

Abstract BACKGROUND Tannins can bind to and precipitate protein by forming insoluble complexes resistant to fermentation and with a positive effect on protein utilisation by ruminants. Three protein types, Rubisco, rapeseed protein and bovine serum albumin (a single high-molecular weight protein), were used to test the effects of increasing concentrations of structurally different condensed tannins on protein solubility/precipitation. RESULTS Protein type (PT) influenced solubility after addition of condensed tannins (P < 0.001) in the order: Rubisco < rapeseed < BSA (P < 0.05). The type of condensed tannin (CT) affected protein solubility (P = 0.001) with a CT × PT interaction (P = 0.001). Mean degree of polymerisation, proportions of cis- versus trans-flavanol subunits or prodelphinidins versus procyanidins among CTs could not explain precipitation capacities. Increasing tannin concentration decreased protein solubility (P < 0.001) with a PT × CT concentration interaction. The proportion of low-molecular weight rapeseed proteins remaining in solution increased with CT concentration but not with Rubisco. CONCLUSIONS Results of this study suggest that PT and CT type are both of importance for protein precipitation but that the CT structures investigated did not allow identification of parameters that contribute most to precipitation. It is possible that the three-dimensional structures of tannins and proteins may be more important factors in tannin–protein interactions. © 2013 Society of Chemical Industry