University, Diss., 2005--Potsdam.

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Der Klimawandel und insbesondere die globale Erwärmung gehören aktuell zu den größten Herausforderungen an Politik und Wissenschaft. Steigende CO2-Emissionen sind hierbei maßgeblich für die Klimaerwärmung verantwortlich. Ein regulierender Faktor beim CO2-Austausch mit der Atmosphäre ist die Vegetation, welche als CO2-Senke aber auch als CO2-Quelle fungieren kann. Diese Funktionen können durch Analysen der Landbedeckungsänderung in Kombination mit Modellierungen der Kohlenstoffbilanz quantifiziert werden, was insbesondere von aktuellen und zukünftigen politischen Instrumenten wie CDM (Clean Development Mechanism) oder REDD (Reducing Emissions from Deforestation and Degradation) gefordert wird. Vor allem in Regionen mit starker Landbedeckungsänderung und hoher Bevölkerungsdichte sowie bei geringem Wissen über die Produktivität und CO2-Speicherpotentiale der Vegetation, bedarf es einer Erforschung und Quantifizierung der terrestrischen Kohlenstoffspeicher. Eine Region, für die dies in besonderem Maße zutrifft, ist Westafrika. Jüngste Studien haben gezeigt, dass sich einerseits die Folgen des Klimawandels und Umweltveränderungen sehr stark in Westafrika auswirken werden und andererseits Bevölkerungswachstum eine starke Änderung der Landbedeckung für die Nutzung als agrarische Fläche bewirkt hat. Folglich sind in dieser Region die terrestrischen Kohlenstoffspeicher durch Ausdehnung der Landwirtschaft und Waldrodung besonders gefährdet. Große Flächen agieren anstelle ihrer ursprünglichen Funktion als CO2-Senke bereits als CO2-Quelle. [...] / Global warming associated with climate change is one of the greatest challenges of today's world. One regulating factor of CO2 exchange with the atmosphere is the vegetation cover. Measurements of land cover changes in combination with modeling of the carbon balance can therefore contribute to determining temporal variations of CO2 sources and sinks, which is an essential necessity of existing and prospective political instruments like CDM (Clean Development Mechanism) or REDD (Reducing Emissions from Deforestation and Degradation). The need for quantifiable terrestrial carbon stocks is especially high for regions, where rates of land cover transformation and population density are high and knowledge on vegetation productivity is low. One region which is characterized by these criteria is West Africa. Therefore, carbon stocks in this region are seriously endangered by land cover change like the expansion of agriculture and forest logging. Large areas already act as carbon sources on a yearly basis instead of their previous function as carbon sink. Since only a few studies have analyzed the terrestrial carbon stocks in Africa and especially regional analysis in West Africa are missing, the following study focuses on regional scale modeling of the actual terrestrial carbon stocks. Additionally, the potential carbon stocks of unmanaged land cover and the potential for CO2 payments have been analyzed in this work. To quantify and assess carbon fluxes as well as the loss of carbon, net primary productivity of vegetation has been modeled, based on the plants characteristics to fix carbon from the atmosphere during photosynthesis. Modeling vegetation dynamics and net primary productivity has been realized by using MODIS 250m time series for semi-humid and semi-arid savanna ecosystems in West Africa. This study aimed to quantify CO2 exchanges of the Savanna regions in the Volta basin by applying and adapting the Regional Biomass Model (RBM). The RBM was developed by Jochen Richters (2005) at a resolution of 1000m for the Namibian Kaokoveld. In this study the model was optimized to the scale of 232m to consider the heterogeneous landscape in West Africa (RBM+). New input parameters with higher accuracies and resolution were generated instead of using the global standard products. The most important parameters for the modeling are FPAR and the fractional cover of herbaceous and woody vegetation. To enhance the MODIS FPAR product, linear interpolation and downscaling algorithms were applied. The main objective of the downscaling is a better representation of the finely scattered vegetation by the 232m resolution FPAR. The second optimized parameter, the fractional cover of herbaceous and woody vegetation was represented by the Vegetation Continuous Fields product (VCF) from MODIS in the originally version of the RBM. This global product reflects the vegetation structure of West Africa poorly, since few high resolution training data is available for this region, and the dynamic savanna vegetation can hardly be classified by not regionally adapted methods. Additionally, the data is only available with 500m resolution. Therefore, in this study a new product with 232m resolution was developed which represents the spatial heterogeneity well and, due to the regional adaptation, shows higher accuracies. The percentage cover of woody and herbaceous vegetation and bare soil on 232m MODIS data was calculated in a multi scale approach. Based on very high resolution data, represented by Quickbird and Ikonos with 0.6-4m resolution, and high resolution data from Landsat with 30m resolution, the percentage coverage was estimated for representative focus regions. These classifications were used as a training data set to determine the percentage coverage on the 232m scale with MODIS time series for the whole study region. Based on these optimized and adapted input parameters, the net primary productivity was modeled. Data from a meteorological station and an Eddy-Covariance-Flux allowed a detailed validation of the input parameters and of the model results. The model led to good results as it only overestimated the net primary productivity for the two analyzed years 2005 and 2006 by 8.8 and 2.0 %, respectively. The second aim of the study was an analysis of the potential for long term terrestrial carbon sinks. Classifications of the actual and of the potential land cover were calculated for this analysis. Considering the overall long time CO2 fixation behavior of trees, which depends on their age, longterm carbon stocks for 100 years were simulated. As carbon fixing could be paid by emission trading, which is in future depending on the political Post-Kyoto programs, potential alternative income was calculated with different price scenarios for the three countries. A comparison with the gross domestic products of these countries and with developing aid, showed the significance of CO2 trading in this region.

Natural gas combined cycles with oxy-fuel combustion is expected tobe an important component of the future carbon constrained energyscenario. An oxy-combustion power cycle enables the fuel to burn in anitrogen free environment and thereby helps separate the CO2 streamfor storage. Depending on the oxygen source and purity, the CO2stream may need further purification via a purification unit (CPU)before compressing it to a high pressure for storage. The major energy penalty in this type of power cycle is the production of oxygenand the downstream purification to remove volatiles. It is this energypenalty which results in the cost of avoiding the CO2 emissions to theatmosphere.Cryogenic Air Separation Units (ASU) for oxygen production con-tribute to approximately 20% of the total energy penalty of such powerplants. Oxygen Transport Membranes (OTM) for oxygen production offers a potential solution to reduce the energy penalty of oxy-combustion natural gas cycles. The energy penalties associated withOTMs are that membranes operate at high temperatures and requirea sweep gas to establish an oxygen partial pressure difference betweenthe feed and permeate streams. Further, while the Cryogenic ASUhas minimum integration with the power process, oxy-combustion cycles with OTMs are tightly integrated with the power plant. Thusthe contributions to efficiency penalty in an OTM-based cycles aredistributed and not easily identified.The objective of the thesis is to answer the question: "Where doesthe plant efficiency loss originate in oxy-combustion CO2 capture process using Oxygen Transport Membrane as compared to one withcryogenic ASU?" The contribution of the work will be to highlight thelosses at the sub-process and at the equipment level.This work studies three different cases of oxy-combustion naturalgas combined cycles (NGCC) with CO2 capture. The baseline scenario, modified/improved scenario and the advanced scenario. Thebaseline scenario is a simple oxy-combustion NGCC power plant withASU as the oxygen source. Various losses associated with this systemare studied in detail. The modified/improved scenario involves analysis of possible modifications to the baseline case and applying theresults in-order to improve the baseline case. The modified scenario isexpected to have a better overall plant performance. The advancedscenario involves usage of OTM for oxygen production.The power plants are simulated in Aspen HYSYS and plant massand heat balances are calculated. Using the stream enthalpy, entropyand composition, we can calculate the stream exergy values. Controlvolumes help us analyze the component and sub-system exergy lossesand arrive at the overall power plant exergetic efficiency. The base-line power plant scheme is found to have an exergetic efficiency of 47percentage points with a thermal efficiency of 49.6 percentage, withcapture.The modified power plant scheme is obtained by increasing the gasturbine pressure ratio and this has a significant impact on the over-all system design and hence the performance. The modified systemhas exergetic and thermal efficiency of 49 and 51 percentage pointsrespectively. The advanced power plant with OTM, also called as theAdvanced Zero Emissions Powerplant (AZEP) has an exergetic efficiency of 51 and a thermal efficiency of 53.4 percentage. In all the cases, the combustor where most of the fuel is burnt is responsible formajority of the exergy destruction.There is potential for improving the ASU and thereby achieving alesser specific oxygen production power and also due to system integration and other improvements, the overall oxy-combustion NGCCpower plant is expected to play an important role in 5 - 10 years. Alsoas the working fluid is different from that of a normal air based powerplant, significant work needs to be done in the gas turbine and compressor part. Also detailed cost estimations, reliability and flexibilitystudies, operability and safety related studies need to be carried outin-order to boost the confidence in oxy-fuel NGCC power plants andtake it to the next phase.

Carbon dioxide CO₂capture through hydrate formation is a novel technology under consideration as an efficient means of separating CO₂from flue/fuel gas mixtures for sequestration and enhanced oil recovery operations. This thesis examines post-combustion capture of CO₂from fossil-fuel power plant flue-gas streams through hydrate formation in a silica gel column. Power plant flue-gas contains essentially CO₂and nitrogen (N2) after suitable pre-treatment steps, thus a model flue-gas comprising 17% co₂and 83% N2 was used in the study. Previous studies employed a stirred-tank reactor to achieve water-gas contact for formation of hydrates; recent microscopic studies involved using water dispersed in silica gel to react with gas, showing potential for improved hydrate formation rates without the need for agitation. This study focuses on macroscopic kinetics of hydrate formation in silica gel to evaluate hydrate formation rates, CO₂separation efficiency and determining optimal silica gel properties as a basis for a CO2 capture process. Spherical silica gels with 30.0 and 100.0 nm pore sizes and 40-75 and 75-200 μm particle sizes were studied to determine pore size and particle size effects on hydrate formation. 100.0 nm pores achieved higher gas uptake and CO₂recovery over the 30.0 nm case. Improved CO₂separation was obtained when 75-200 μm particles with 100.0 nm pores were used. The two effects observed are due to improved gas diffusion occurring with larger pore and particle size, favouring increased hydrate formation. Compared to stirred-tank experiments, results in this study show a near four-fold increase in moles of gas incorporated in the hydrate per mole of water, showing that improved water-to-hydrate conversion is obtained with pore-dispersed water. At similar experimental conditions, CO₂recovery improved from 42% for stirred-tank studies to 51% for the optimum silica (100.0 nm 75-200 μm) determined in this study. Finally, effects of tetrahydrofuran (THF) - an additive that reduces operating pressure were evaluated. Experiments with 1 mol% THF, the optimum determined from previous stirred tank studies, showed improved gas consumption in silica but reduced CO₂recovery, indicating that the optimum concentration for use in silica is different from that in stirred-tank experiments.

A multidisciplinary approach has been applied to the development of sustainable technologies for three industrially relevant projects. Reversible ionic liquids are novel carbon dioxide capture solvents. These non-aqueous silylamines efficiently capture carbon dioxide through chemical and physical absorption and release carbon dioxide with minimal addition of heat. The development of these capture agents aims to eliminate the need for a co-solvent, while minimizing energy loss and achieving solvent recyclability. Also presented is the use of carbon dioxide for amine protection during chemical syntheses. Amine protection is widely used in almost all sectors of chemical and pharmaceutical industries. The use of carbon dioxide as a reversible protecting group reduces solvent waste during protection and deprotection and improves the atom economy of existing processes. Sustainable chemistry has also been applied to the use of reversible ionic liquids as switchable surfactants for nanoparticle synthesis. The reversible ionic liquid system offers two significant advantages toward a more efficient synthesis and deposition of nanoparticles in that an additional surfactant is not required, and due to the reversible nature of the ionic liquids, a facile and waste-reduced deposition method exists.

Carbon dioxide CO₂capture through hydrate formation is a novel technology under consideration as an efficient means of separating CO₂from flue/fuel gas mixtures for sequestration and enhanced oil recovery operations. This thesis examines post-combustion capture of CO₂from fossil-fuel power plant flue-gas streams through hydrate formation in a silica gel column. Power plant flue-gas contains essentially CO₂and nitrogen (N2) after suitable pre-treatment steps, thus a model flue-gas comprising 17% co₂and 83% N2 was used in the study. Previous studies employed a stirred-tank reactor to achieve water-gas contact for formation of hydrates; recent microscopic studies involved using water dispersed in silica gel to react with gas, showing potential for improved hydrate formation rates without the need for agitation. This study focuses on macroscopic kinetics of hydrate formation in silica gel to evaluate hydrate formation rates, CO₂separation efficiency and determining optimal silica gel properties as a basis for a CO2 capture process. Spherical silica gels with 30.0 and 100.0 nm pore sizes and 40-75 and 75-200 μm particle sizes were studied to determine pore size and particle size effects on hydrate formation. 100.0 nm pores achieved higher gas uptake and CO₂recovery over the 30.0 nm case. Improved CO₂separation was obtained when 75-200 μm particles with 100.0 nm pores were used. The two effects observed are due to improved gas diffusion occurring with larger pore and particle size, favouring increased hydrate formation. Compared to stirred-tank experiments, results in this study show a near four-fold increase in moles of gas incorporated in the hydrate per mole of water, showing that improved water-to-hydrate conversion is obtained with pore-dispersed water. At similar experimental conditions, CO₂recovery improved from 42% for stirred-tank studies to 51% for the optimum silica (100.0 nm 75-200 μm) determined in this study. Finally, effects of tetrahydrofuran (THF) - an additive that reduces operating pressure were evaluated. Experiments with 1 mol% THF, the optimum determined from previous stirred tank studies, showed improved gas consumption in silica but reduced CO₂recovery, indicating that the optimum concentration for use in silica is different from that in stirred-tank experiments.

Carbon dioxide CO₂capture through hydrate formation is a novel technology under consideration as an efficient means of separating CO₂from flue/fuel gas mixtures for sequestration and enhanced oil recovery operations. This thesis examines post-combustion capture of CO₂from fossil-fuel power plant flue-gas streams through hydrate formation in a silica gel column. Power plant flue-gas contains essentially CO₂and nitrogen (N2) after suitable pre-treatment steps, thus a model flue-gas comprising 17% co₂and 83% N2 was used in the study. Previous studies employed a stirred-tank reactor to achieve water-gas contact for formation of hydrates; recent microscopic studies involved using water dispersed in silica gel to react with gas, showing potential for improved hydrate formation rates without the need for agitation. This study focuses on macroscopic kinetics of hydrate formation in silica gel to evaluate hydrate formation rates, CO₂separation efficiency and determining optimal silica gel properties as a basis for a CO2 capture process. Spherical silica gels with 30.0 and 100.0 nm pore sizes and 40-75 and 75-200 μm particle sizes were studied to determine pore size and particle size effects on hydrate formation. 100.0 nm pores achieved higher gas uptake and CO₂recovery over the 30.0 nm case. Improved CO₂separation was obtained when 75-200 μm particles with 100.0 nm pores were used. The two effects observed are due to improved gas diffusion occurring with larger pore and particle size, favouring increased hydrate formation. Compared to stirred-tank experiments, results in this study show a near four-fold increase in moles of gas incorporated in the hydrate per mole of water, showing that improved water-to-hydrate conversion is obtained with pore-dispersed water. At similar experimental conditions, CO₂recovery improved from 42% for stirred-tank studies to 51% for the optimum silica (100.0 nm 75-200 μm) determined in this study. Finally, effects of tetrahydrofuran (THF) - an additive that reduces operating pressure were evaluated. Experiments with 1 mol% THF, the optimum determined from previous stirred tank studies, showed improved gas consumption in silica but reduced CO₂recovery, indicating that the optimum concentration for use in silica is different from that in stirred-tank experiments. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

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Flue gas carbon dioxide emissions from coal-based power plants are suggested as a factor causing climate change. Membrane is an attractive technology for the capture of carbon dioxide from flue gas. Matrimid® asymmetric hollow fiber membranes with “homogeneous dense” and “fused nodular” selective layers were successfully formed. The PDMS post-treated nodular-skinned fibers showed better cold performance than the dense-skinned fibers with bore side feed. A hypothesis with regards to increased sorption capacity coupled with orientated polymer chain segments for the nodular skin was proposed and supported by indirect evidences. Based on the understanding of CO2 and N2 transport in cold Matrimid® hollow fiber membranes, a second generation of cold membranes with superior performance was developed. The high free volume, rigid 6FDA/BPDA-DAM hollow fiber membranes with both dense and nodular selective layers were successfully formed as well, which showed similar selectivity but much higher permeance than the high performing nodular Matrimid® hollow fiber membranes at cold conditions.