Zur Reaktionskinetik der Oxidation von Kohlenstoffmaterialien aus Biomasse

Zur Modellierung von Vergasungs- und Verbrennungsprozessen zur energetischen Nutzung von Biomasse ist die Kenntnis von reaktionskinetischen Daten für die Sauerstoff-Oxidation von Biomassepyrolysaten erforderlich. Eine ausführliche Literaturübersicht zeigt den Stand der Forschung bezüglich der experimentellen Ermittlung von reaktionskinetischen Parametern für die Oxidation von Pyrolysaten aus Lignin, Cellulose und pflanzlicher Biomasse sowie der Suche nach einem plausiblen Reaktionsmechanismus für die Reaktion von Sauerstoff mit festen Kohlenstoffmaterialien. Es wird eine Versuchsanlage mit einem quasistationär betriebenen Differentialreaktor konstruiert, die eine Messung der Reaktionskinetik und der reaktiven inneren Oberfläche (RSA) für die Reaktion eines Pyrolysats aus Maispflanzen mit Sauerstoff ermöglicht. Die getrockneten und zerkleinerten Maispflanzen werden 7 Minuten lang bei 1073 K in einem Drehrohrofen pyrolysiert. Das Pyrolysat zeichnet sich vor allem durch seine hohe Porosität von über 0,9 und seinen hohen Aschegehalt von 0,24 aus. Die RSA wird nach der Methode der Messung von Übergangskinetiken (TK) bestimmt. Die Bestimmung der RSA erfolgt für die Reaktionsprodukte CO und CO2 getrennt, für die entsprechend ermittelten Werte werden die Bezeichnungen CO-RSA und CO2-RSA eingeführt. Die Abhängigkeit dieser Größen von der Sauerstoffkonzentration läßt sich durch eine Langmuir-Isotherme beschreiben, ebenso das leichte Absinken der CO-RSA mit der Kohlendioxidkonzentration. Über dem Abbrand zeigen sich unterschiedliche Verläufe für die CO-RSA, CO2-RSA und die innere Oberfläche nach der BET-Methode. Zur Charakterisierung der Oberflächenzwischenprodukte werden temperaturprogrammierte Desorptionsversuche (TPD) durchgeführt. Die Ergebnisse zeigen, daß eine Unterscheidung in zwei Kohlenstoff-Sauerstoff-Oberflächenkomplexe ausreichend ist. Die experimentellen Untersuchungen zum Oxidationsverlauf werden im kinetisch bestimmten Bereich durchgeführt. Dabei werden die Parameter Temperatur, Sauerstoff-, CO- und CO2-Konzentration variiert. Anhand der Ergebnisse der reaktionskinetischen Untersuchungen wird ein Reaktionsmechanismus für die Kohlenstoff-Sauerstoff-Reaktion entwickelt. Dieser Reaktionsmechanismus umfaßt 7 Elementarreaktionen, für welche die reaktionskinetischen Parameter numerisch ermittelt werden. Darüber hinaus werden reaktionskinetische Parameter für einfachere massenbezogene Reaktionsgeschwindigkeitsansätze berechnet und summarische Reaktionsgeschwindigkeitsansätze für die Bildung von CO und CO2 aus dem Reaktionsmechanismus hergeleitet.

Theory for the Photoacoustic Response to X-Ray Absorption

A microscopic theory is presented for the photoacoustic effect induced in solids by x-ray absorption. The photoacoustic effect results from the thermalization of the excited Auger electrons and photoelectrons. We explain the dependence of the photoacoustic signal S on photon energy and the proportionality to the x-ray absorption coefficient in agreement with recent experiments on Cu. Results are presented for the dependence of S on photon energy, sample thickness, and the electronic structure of the absorbing solid.

Relativistic effects in physics and chemistry of element 105. [Part] IV.

Results of relativistic (Dirac-Slater and Dirac-Fock) and nonrelativistic (Hartree-Fock-Slater) atomic and molecular calculations have been compared for the group 5 elements Nb, Ta, and Ha and their compounds MCl_5, to elucidate the influence of relativistic effects on their properties especially in going from the 5d element Ta to the 6d element Ha. The analysis of the radial distribution of the valence electrons of the metals for electronic configurations obtained as a result of the molecular calculations and their overlap with ligands show opposite trends in behavior for ns_1/2, np_l/2, and (n -1 )d_5/2 orbitals for Ta and Ha in the relativistic and nonrelativistic cases. Relativistic contraction and energetic stabilization of the ns_1/2 and np_l/2 wave functions and expansion and destabilization of the (n-1)d_5/2 orbitals make hahnium pentahalide more covalent than tantalum pentahalide and increase the bond strength. The nonrelativistic treatment of the wave functions results in an increase in ionicity of the MCl_5 molecules in going from Nb to Ha making element Ha an analog of V. Different trends for the relativistic and nonrelativistic cases are also found for ionization potentials, electronic affinities, and energies of charge-transfer transitions as well as the stability of the maximum oxidation state.

Molecular photochemistry with femtosecond laser pulses

Femtosecond laser pulses generated from an amplified coiliding pulse modelocked ring dye laser have been employed in molecular beam experiments to study the dynamics and the pathways of multiphoton induced ionization, autoionization and fragmentation of Na2 . Energy distributions of photoelectrons arising from these processes and the mass and released kinetic energy of the corresponding fragment ions are measured by time-of-flight spectroscopy.

Orgodynamik als Konzept und Methode einer transpersonal orientierten Forschungs- und Lehrpraxis pädagogisch-psychologischer Bewusstseinsschulung in der Erwachsenenbildung

In der vorliegenden Dissertation geht es um die Dokumentation, theoretische Begründung und Auswertung des in 25 Jahren Praxis entwickelten Curriculums der Bewusstseinsschulung und -weitung der Orgodynamik. Dabei geht es insbesondere um den Vergleich und die forschungsorientierte Verknüpfung verschiedener Traditionen der Bewusstseinsbildung, der ihnen zugrunde liegenden Konzepte und anthropologischen Dimensionen im Schnittfeld pädagogischer, psychologischer und spiritueller Perspektiven. In Anlehnung an das von Fuhr/Dauber (2002) entwickelte Modell, der Praxisentwicklungsforschung, welche die Verflechtung von Theorie und Praxis ansteuert, wird der orgodynamische Ansatz wissenschaftlich dokumentiert und theoretisch begründet. Über eine induktive Vorgehensweise werden die historischen Wurzeln konzeptionell dargelegt, die verborgenen Paradigmen herausgearbeitet, sowie das Curriculum erläutert und ausgewertet. In einem ersten theorieorientierten Kapitel wird das orgodynamische Methodenspektrum in seinem Grundmodell und den vier zentralen Dimensionen (mentale, körperliche, emotionale, energetische Dimension) aufgezeigt und mit theoretischen Hintergrundkonzepten verglichen und verknüpft. Die vier sich überlappenden Methodengruppen der mental, körperlich, emotional und energetisch orientierten Bewusstseinsarbeit werden differenziert dargestellt und in ihrer Beziehung zueinander diskutiert. Anhand eines Modells (Methodenrad) wird die multi-dimensionale Perspektive des Methodenspektrums, in einer nichthierarchischen Zuordnung sichtbar. Im zweiten theorieorientierten Hauptteil werden zunächst die zentralen vier Paradigmen der Orgodynamik (Präsenz, Multidimensionalität, Flow/Fließendes Gewahrsein, Bezogenheit) vorgestellt, theoretisch und praxisbezogen entfaltet und in einer Paradigmen-Landkarte zueinander in Beziehung gesetzt. Dabei werden die kategorialen Ausführungen durchgehend an Praxisbeispielen veranschaulicht und im Blick auf drei vorgestellte Zugänge zur Bewusstseinsweitung (Immersion, Integration und Dekonstruktion) exemplarisch didaktisch kommentiert. Im dritten Hauptteil wird das Curriculum im Zusammenhang mit einer Auswertungsmatrix erläutert. Diese dient als Überprüfungsinstrument. Mit ihrer Hilfe werden die verschiedenen methodischen Zugangsweisen und Arbeitsformen dieses Ansatzes, exemplarisch anhand von 2 Ausbildungswochen, im Blick der Multidimensionalität dokumentiert. Damit wird diese multidimensional angelegte Praxis exemplarisch bis in methodische Details nachvollziehbar und in dialogisch-selbstreflexiver Form überprüfbar. Exemplarisch werden in einem Exkurs erste Itemvorschläge gemacht, welche die wissenschaftliche Anschlussfähigkeit an neuere Forschung im transpersonalen Bereich aufzeigen. Das innere Anliegen der vorliegenden Arbeit zeigt in der Verschränkung von Theorie und Praxis, dass die Paradigmen der Orgodynamik, Präsenz, Multidimensionalität, fließendes Gewahrsein und bewusste Bezogenheit vier pädagogisch umgesetzte Paradigmen für eine Bewusstseinserforschung in der Erwachsenenbildung sind. Stichworte: Multidimensional, Bewusstseinserforschung, Bewusstseinsweite, Präsenz, bewusste Bezogenheit, Flow/Fließendes Gewahrsein, das „Größere“, Immersion, Integration, Dekonstruktion, pädagogische Paradigmen, Erwachsenenbildung, Multidimensionales Methodenspektrum, Orgodynamik, Körpertherapie. ---------------------------

Economics of Hybrid Photovoltaic Power Plants

The global power supply stability is faced to several severe and fundamental threats, in particular steadily increasing power demand, diminishing and degrading fossil and nuclear energy resources, very harmful greenhouse gas emissions, significant energy injustice and a structurally misbalanced ecological footprint. Photovoltaic (PV) power systems are analysed in various aspects focusing on economic and technical considerations of supplemental and substitutional power supply to the constraint conventional power system. To infer the most relevant system approach for PV power plants several solar resources available for PV systems are compared. By combining the different solar resources and respective economics, two major PV systems are identified to be very competitive in almost all regions in the world. The experience curve concept is used as a key technique for the development of scenario assumptions on economic projections for the decade of the 2010s. Main drivers for cost reductions in PV systems are learning and production growth rate, thus several relevant aspects are discussed such as research and development investments, technical PV market potential, different PV technologies and the energetic sustainability of PV. Three major market segments for PV systems are identified: off-grid PV solutions, decentralised small scale on-grid PV systems (several kWp) and large scale PV power plants (tens of MWp). Mainly by application of ‘grid-parity’ and ‘fuel-parity’ concepts per country, local market and conventional power plant basis, the global economic market potential for all major PV system segments is derived. PV power plant hybridization potential of all relevant power technologies and the global power plant structure are analyzed regarding technical, economical and geographical feasibility. Key success criteria for hybrid PV power plants are discussed and comprehensively analysed for all adequate power plant technologies, i.e. oil, gas and coal fired power plants, wind power, solar thermal power (STEG) and hydro power plants. For the 2010s, detailed global demand curves are derived for hybrid PV-Fossil power plants on a per power plant, per country and per fuel type basis. The fundamental technical and economic potentials for hybrid PV-STEG, hybrid PV-Wind and hybrid PV-Hydro power plants are considered. The global resource availability for PV and wind power plants is excellent, thus knowing the competitive or complementary characteristic of hybrid PV-Wind power plants on a local basis is identified as being of utmost relevance. The complementarity of hybrid PV-Wind power plants is confirmed. As a result of that almost no reduction of the global economic PV market potential need to be expected and more complex power system designs on basis of hybrid PV-Wind power plants are feasible. The final target of implementing renewable power technologies into the global power system is a nearly 100% renewable power supply. Besides balancing facilities, storage options are needed, in particular for seasonal power storage. Renewable power methane (RPM) offers respective options. A comprehensive global and local analysis is performed for analysing a hybrid PV-Wind-RPM combined cycle gas turbine power system. Such a power system design might be competitive and could offer solutions for nearly all current energy system constraints including the heating and transportation sector and even the chemical industry. Summing up, hybrid PV power plants become very attractive and PV power systems will very likely evolve together with wind power to the major and final source of energy for mankind.

Alley cropping of willows and grassland for bioenergy provision: productivity, tree-crop interactions and energy balance

The demand for biomass for bioenergy has increased rapidly in industrialized countries in the recent years. Biogenic energy carriers are known to reduce CO2 emissions. However, the resource-inefficient production of biomass often caused negative impacts on the environment, e.g. biodiversity losses, nitrate leaching, and erosion. The detrimental effects evolved mainly from annual crops. Therefore, the aim of modern bioenergy cropping systems is to combine yield stability and environmental benefits by the establishment of mixed-cropping systems. A particular emphasis is on perennial crops which are perceived as environmentally superior to annual crops. Agroforestry systems represent such mixed perennial cropping systems and consist of a mix of trees and arable crops or grassland within the same area of land. Agroforestry practices vary across the globe and alley cropping is a type of agroforestry system which is well adapted to the temperate zone, with a high degree of mechanization. Trees are planted in rows and crops are planted in the alleyways, which facilitates their management by machinery. This study was conducted to examine a young alley cropping system of willows and two grassland mixtures for bioenergy provision under temperate climate conditions. The first part of the thesis identified possible competition effects between willows and the two grassland mixtures. Since light seemed to be the factor most affecting the yield performance of the understory in temperate agroforestry systems, a biennial in situ artificial shade experiment was established over a separate clover-grass stand to quantify the effects of shade. Data to possible below- and aboveground interactions among willows and the two grassland mixtures and their effects on productivity, sward composition, and quality were monitored along a tree-grassland interface within the alleys. In the second part, productivity of the alley cropping system was examined on a triennial time frame and compared to separate grassland and willow stands as controls. Three different conversion technologies (combustion of hay, integrated generation of solid fuel and biogas from biomass, whole crop digestion) were applied to grassland biomass as feedstock and analyzed for its energetic potential. The energetic potential of willow wood chips was calculated by applying combustion as conversion technique. Net energy balances of separate grassland stands, agroforestry and pure willow stands evaluated their energy efficiency. Results of the biennial artificial shade experiment showed that severe shade (80 % light reduction) halved grassland productivity on average compared to a non-shaded control. White clover as heliophilous plant responded sensitively to limited radiation and its dry matter contribution in the sward decreased with increasing shade, whereas non-leguminous forbs (mainly segetal species) benefited. Changes in nutritive quality could not be confirmed by this experiment. Through the study on interactions within the alleys of the young agroforestry system it was possible to outline changes of incident light, soil temperature and sward composition of clover-grass along the tree-grassland interface. Nearly no effects of trees on precipitation, soil moisture and understory productivity occurred along the interface during the biennial experiment. Considering the results of the productivity and the net energy yield alley cropping system had lower than pure grassland stands, irrespective of the grassland seed mixture or fertilization, but was higher than that for pure willow stands. The comparison of three different energetic conversion techniques for the grassland biomass showed highest net energy yields for hay combustion, whereas the integrated generation of solid fuel and biogas from biomass (IFBB) and whole crop digestion performed similarly. However, due to the low fuel quality of hay, its direct combustion cannot be recommended as a viable conversion technique, whereas IFBB fuels were of a similar quality to wood chip from willow.

Integrated bioenergy and food production

Rising global energy needs and limited fossil fuel reserves have led to increased use of renewable energies. In Germany, this has entailed massive exploitation of agricultural biomass for biogas generation, associated with unsustainable farming practices. Organic agriculture not only reduces negative environmental impacts, organic farmers were also prime movers in anaerobic digestion (AD) in Germany. This study’s aim was to identify the structure, development, and characteristics of biogas production associated with organic farming systems in order to estimate further development, as well as energetic and associated agronomic potentials. Surveys were conducted among organic farms with AD technology. 144 biogas plants could be included in the analysis. Total installed electrical capacity was 30.8 MWel, accounting for only 0.8% of the total installed electrical capacity in the German biogas sector. Recently, larger plant types (>250 kWel) with increased use of (also purchased) energy crops have emerged. Farmers noticed increases in yields (22% on average) and quality of cash crops in arable farming through integrated biogas production. In conclusion, although the share of AD in organic farming is relatively small it can provide various complementary socio-ecological benefits such as the enhancement of food output through digestate fertilization without additional need for land, while simultaneously reducing greenhouse gas emissions from livestock manures and soils. However, to achieve this eco-functional intensification, AD systems and their management have to be well adapted to farm size and production focus and based primarily on residue biomass.