Multivariate NIR studies of seed-water interaction in Scots Pine Seeds (Pinus sylvestris L.)

This thesis describes seed-water interaction using near infrared (NIR) spectroscopy, multivariate regression models and Scots pine seeds. The presented research covers classification of seed viability, prediction of seed moisture content, selection of NIR wavelengths and interpretation of seed-water interaction modelled and analysed by principal component analysis, ordinary least squares (OLS), partial least squares (PLS), bi-orthogonal least squares (BPLS) and genetic algorithms. The potential of using multivariate NIR calibration models for seed classification was demonstrated using filled viable and non-viable seeds that could be separated with an accuracy of 98-99%. It was also shown that multivariate NIR calibration models gave low errors (0.7% and 1.9%) in prediction of seed moisture content for bulk seed and single seeds, respectively, using either NIR reflectance or transmittance spectroscopy. Genetic algorithms selected three to eight wavelength bands in the NIR region and these narrow bands gave about the same prediction of seed moisture content (0.6% and 1.7%) as using the whole NIR interval in the PLS regression models. The selected regions were simulated as NIR filters in OLS regression resulting in predictions of the same quality (0.7 % and 2.1%). This finding opens possibilities to apply NIR sensors in fast and simple spectrometers for the determination of seed moisture content. Near infrared (NIR) radiation interacts with overtones of vibrating bonds in polar molecules. The resulting spectra contain chemical and physical information. This offers good possibilities to measure seed-water interactions, but also to interpret processes within seeds. It is shown that seed-water interaction involves both transitions and changes mainly in covalent bonds of O-H, C-H, C=O and N-H emanating from ongoing physiological processes like seed respiration and protein metabolism. I propose that BPLS analysis that has orthonormal loadings and orthogonal scores giving the same predictions as using conventional PLS regression, should be used as a standard to harmonise the interpretation of NIR spectra

Gasification of pure and mixed feedstock components: Effect on syngas composition and gasification efficiency

The aim of this work was to investigate whether the use of individual tree components (i.e., stem wood, bark, branches, and needles of spruces) as feedstocks during oxygen blow gasification is more efficient than using mixtures of these components. Experiments were performed at three oxygen levels in an 18-kW oxygen blown fixed bed gasifier with both single and mixed component feedstocks. The composition of the resulting syngas and the cold gas efficiency based on CO and H-2 (CGE(fuel)) were used as response variables to evaluate the influence of different feedstocks on gasification performance. Based on the experimental results and data on the composition of similar to 26000 trees drawn from a national Swedish spruce database, multivariate models were developed to simulate gasifier performance under different operating conditions and with different feedstock compositions. The experimental results revealed that the optimal CGE(fuel) with respect to the oxygen supply differed markedly between the different spruce tree components. Additionally, the models showed that co-gasification of mixed components yielded a lower CGE(fuel )than separate gasification of pure components. Optimizing the oxygen supply for the average tree composition reduced the CGE(fuel) by 1.3-6.2% when compared to optimal gasification of single component feedstocks. Therefore, if single-component feedstocks are available, it may be preferable to gasify them separately because doing so provides a higher gasification efficiency than co-gasification of mixed components

Shiitake cultivation as biological preprocessing of lignocellulosic feedstocks-Substrate changes in crystallinity, syringyl/guaiacyl lignin and degradation-derived by-products

Formulation of substrates based on three hardwood species combined with modulation of nitrogen content by whey addition (0-2%) was investigated in an experiment designed in D-optimal model for their effects on biological preproceesing of lignocellulosic feedstock by shiitake mushroom (Lentinula edodes) cultivation. Nitrogen loading was shown a more significant role than wood species for both mushroom production and lignocellulose degradation. The fastest mycelial colonisation occurred with no nitrogen supplementation, but the highest mushroom yields were achieved when 1% whey was added. Low nitrogen content resulted in increased delignification and minimal glucan consumption. Delignification was correlated with degradation of syringyl lignin unit, as indicated by a significant reduction (41.5%) of the syringyl-to-guaiacyl ratio after cultivation. No significant changes in substrate crystallinity were observed. The formation of furan aldehydes and aliphatic acids was negligible during the pasteurisation and fungal cultivation, while the content of soluble phenolics increased up to seven-fold

Fate of phosphorus and potassium in single-pellet thermal conversion of forest residues with a focus on the char composition

The phosphorus and potassium contents of the char obtained from thermal conversion of forest residues can limit its utilization as an alternative fuel and reducing agent to substitute coal/coke in the steelmaking industry. In this study, ash transformation and release of K and P during single-pellet thermal conversion of different types of forest residues (i.e., bark, twigs, and bark+twigs) were investigated with the aid of a vertical tube furnace (Macro-TGA) at different temperatures (i.e., 600, 800, and 950 degrees C) and within and after different fuel conversion stages, i.e., devolatilization and char gasification. The residual char before and after full devolatilization, and ash after char gasification were characterized by SEM-EDS, XRD, and ICP-OES with the support of thermochemical equilibrium calculations. The concentrations of K (7970-19500 mg/kg) and P (1440-4925 mg/kg) in the char produced after devolatilization were more than four times higher than in coke and pulverized coal frequently used in metallurgical processes. A low amount of P and K (<= 15%) were released from all fuels. K and P were evenly distributed within the char residues, and no crystalline compounds containing K and P were found. In ash residues of bark, K was found in K2Ca2(CO3)3, and K2Ca(CO3)2. K in ash residues from twigs and bark+twigs was mainly found in the amorphous part of ash, most likely in the form of K-Ca rich silicates. Apatite was found as the main P crystalline compound in all ashes at all temperatures. Estimations show that a release of more than 80% is needed for the studied forest residual assortments to reach K and P concentrations typical of blast furnace coals and cokes

NIR provides excellent predictions of properties of biocoal from torrefaction and pyrolysis of biomass

When biomass is exposed to high temperatures in torrefaction, pyrolysis or gasification treatments, the enrichment of carbon in the remaining 'green coal' is correlated with the temperature. Various other properties, currently measured using wet chemical methods, which affect the materials' quality as a fuel, also change. The presented study investigated the possibility of using NIR spectrometry to estimate diverse variables of biomass originating from two sources (above-ground parts of reed canary grass and Norway spruce wood) carbonised at temperatures ranging from 240 to 850 C-circle. The results show that the spectra can provide excellent predictions of its energy, carbon, oxygen, hydrogen, ash, volatile matter and fixed carbon contents. Hence NIR spectrometry combined with multivariate calibration modeling has potential utility as a standardized method for rapidly characterising thermo-treated biomass, thus reducing requirements for more costly, laborious wet chemical analyses and consumables

Biomass particle design through cyclone treatment

Two different forest chip assortments were treated in an air-blown cyclone. Through cyclone treatment, particle sizes and particle distribution widths were decreased. For one of the assortments, due to splitting along the grain, particle sphericity was decreased and flow properties were impaired. For the other assortment, as a consequence of rough edge wear-off of particles, sphericity was increased and flow properties improved.</p

NIR provides excellent predictions of properties of biocoal from torrefaction and pyrolysis of biomass

When biomass is exposed to high temperatures in torrefaction, pyrolysis or gasification treatments, the enrichment of carbon in the remaining 'green coal' is correlated with the temperature. Various other properties, currently measured using wet chemical methods, which affect the materials' quality as a fuel, also change. The presented study investigated the possibility of using NIR spectrometry to estimate diverse variables of biomass originating from two sources (above-ground parts of reed canary grass and Norway spruce wood) carbonised at temperatures ranging from 240 to 850 C-circle. The results show that the spectra can provide excellent predictions of its energy, carbon, oxygen, hydrogen, ash, volatile matter and fixed carbon contents. Hence NIR spectrometry combined with multivariate calibration modeling has potential utility as a standardized method for rapidly characterising thermo-treated biomass, thus reducing requirements for more costly, laborious wet chemical analyses and consumables

Biomass particle design through cyclone treatment

Two different forest chip assortments were treated in an air-blown cyclone. Through cyclone treatment, particle sizes and particle distribution widths were decreased. For one of the assortments, due to splitting along the grain, particle sphericity was decreased and flow properties were impaired. For the other assortment, as a consequence of rough edge wear-off of particles, sphericity was increased and flow properties improved.</p

Analysis, pretreatment and enzymatic saccharification of different fractions of Scots pine

Background: Forestry residues consisting of softwood are a major lignocellulosic resource for production of liquid biofuels. Scots pine, a commercially important forest tree, was fractionated into seven fractions of chips: juvenile heartwood, mature heartwood, juvenile sapwood, mature sapwood, bark, top parts, and knotwood. The different fractions were characterized analytically with regard to chemical composition and susceptibility to dilute-acid pretreatment and enzymatic saccharification. Results: All fractions were characterized by a high glucan content (38-43%) and a high content of other carbohydrates (11-14% mannan, 2-4% galactan) that generate easily convertible hexose sugars, and by a low content of inorganic material (0.2-0.9% ash). The lignin content was relatively uniform (27-32%) and the syringyl-guaiacyl ratio of the different fractions were within the range 0.021-0.025. The knotwood had a high content of extractives (9%) compared to the other fractions. The effects of pretreatment and enzymatic saccharification were relatively similar, but without pretreatment the bark fraction was considerably more susceptible to enzymatic saccharification. Conclusions: Since sawn timber is a main product from softwood species such as Scots pine, it is an important issue whether different parts of the tree are equally suitable for bioconversion processes. The investigation shows that bioconversion of Scots pine is facilitated by that most of the different fractions exhibit relatively similar properties with regard to chemical composition and susceptibility to techniques used for bioconversion of woody biomass