Adsorptive desulfurization is a promising technology to provide sulfur free fuels for fuel cell based power units. In this work the adsorption kinetics of three different aromatic sulfur heterocycles was studied for Ag-Al₂O₃. The influence of individual as well as competitive adsorption on the selectivity order was investigated by equilibrium and breakthrough experiments. In these experiments a jet-A1 fuel enriched with benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was used. The adsorption of aromatic sulfur heterocycles on Ag-Al₂O₃ proceeds via three different adsorption mechanisms. Within these mechanisms the π-interaction (π-Ag) and the direct sulfur-silver interaction (S-Ag) are significantly stronger in comparison to the acid base interaction (S-H). The results showed that the π-Ag and S-Ag interactions are the major adsorption mechanisms in the first stage, where film-diffusion limits the adsorption rate. In the second stage, the S-H interaction plays only an important role for BT, where intraparticle diffusion is the rate controlling step. The overall selectivity order was found to be BT > DBT > 4,6-DMDBT in the case of competitive adsorption for both equilibrium and breakthrough performance. The S-H contribution was related to incorporation of silver into blank γ-alumina, which significantly increased the overall acidity of the adsorbent.

Solar-assisted heating systems use the energy of the sun to supply consumers with renewable heat and can be found all over the world where heating of buildings is necessary. For these systems, both heat production and heat demand are directly related to the weather conditions. In order to optimally plan production, storage, and consumption, forecasts for both the future heat production of the thermal solar collectors as well as the future heat demand of the connected consumers are essential. For this reason, this contribution presents adaptive forecast methods for the solar heat production and the heat demand of consumers using weather forecasts. The developed methods are easy to implement and therefore practically applicable. The final verification of the methods shows good agreement between the predicted values and measurement data from a representative solar-assisted heating system.

Adsorptive on-board desulfurization units require a high desulfurization and regeneration performance for a wide range of fuels to keep them small and ensure long maintenance intervals. A novel thermal regeneration strategy was investigated in this work, fulfilling all requirements for in situ on-board regeneration. In this strategy, a temperature-controlled flow rate (TCFR) of air was used to control the temperature inside the adsorber. With this dynamic approach, the regeneration time was reduced significantly in comparison to other thermal regeneration strategies. The novel regeneration strategy was tested using Ag–Al₂O₃ as an adsorbent to desulfurize a benzothiophen (BT)-enriched road diesel (300 ppmw of total sulfur). A commercial diesel containing fatty acid methyl ester (FAME) was used to evaluate the fuel flexibility regarding desulfurization and regeneration performance. In the case of 6.63 wt % FAME and 300 ppmw of sulfur, the breakthrough adsorption capacity of sulfur decreased from 1.04 to 0.17 mg/g. In TCFR regeneration experiments, the breakthrough adsorption capacity was restored to over 94% in the case of both fuels. Thereby, the Brunauer–Emmett–Teller (BET) surface area of the regenerated adsorbent decreased by only 1.5%, and negligible carbon deposits were detected.

On-board desulfurization is essential to operate fuel-cell-based auxiliary power units (APU) with commercial fuels. In this work, both (i) on-board desulfurization and (ii) on-board regeneration performance of Ag-Al₂O₃ adsorbent is investigated in a comprehensive manner. The herein investigated regeneration strategy uses hot APU off-gas as the regeneration medium and requires no additional reagents, tanks, nor heat exchangers and thus has remarkable advantages in comparison to state-of-the-art regeneration strategies. The results for (i) show high desulfurization performance of Ag-Al₂O₃ under all relevant operating conditions and specify the influence of individual operation parameters and the combination of them, which have not yet been quantified. The system integrated regeneration strategy (ii) shows excellent regeneration performance recovering 100% of the initial adsorption capacity for all investigated types of fuels and sulfur heterocycles. Even the adsorption capacity of the most challenging dibenzothiophene in terms of regeneration is restored to 100% over 14 cycles of operation. Subsequent material analyses proved the thermal and chemical stability of all relevant adsorption sites under APU off-gas conditions. To the best of our knowledge, this is the first time 100% regeneration after adsorption of dibenzothiophene is reported over 14 cycles of operation for thermal regeneration in oxidizing atmospheres.

To examine relevant combustion characteristics of biomass fuels in grate combustion systems, a specially designed lab-scale reactor was developed. On the basis of tests performed with this reactor, information regarding the biomass decomposition behavior, the release of NO_x precursor species, the release of ash-forming elements, and first indications concerning ash melting can be evaluated. Within the scope of several projects, the lab-scale reactor system as well as the subsequent evaluation routines have been optimized and tests with a considerable number of different biomass fuels have been performed. These tests comprised a wide variation of different fuels, including conventional wood fuels (beech, spruce, and softwood pellets), bark, wood from short rotation coppice (SRC) (poplar and willow), waste wood, torrefied softwood, agricultural biomass (straw, Miscanthus, maize cobs, and grass pellets), and peat and sewage sludge. The results from the lab-scale reactor tests show that the thermal decomposition behavior and the combustion behavior of different biomass fuels vary considerably. With regard to NO_x precursors (NH_x, HCN, NO, N₂O, and NO₂), NH₃ and, for chemically untreated wood fuels, also HCN represent the dominant nitrogen species. The conversion rate from N in the fuel to N in NO_x precursors varies between 20 and 95% depending upon the fuel and generally decreases with an increasing N content of the fuel. These results gained from the lab-scale reactor tests can be used to derive NO_x precursor release models for subsequent computational fluid dynamics (CFD) NO_x post-processing. The release of ash-forming vapors also considerably depends upon the fuel used. In general, more than 91% of Cl, more than 71% of S, 1-51% of K, and 1-50% of Na are released to the gas phase. From these data, the potential for aerosol emissions can be estimated, which varies between 18 mg/Nm³ (softwood pellets) and 320 mg/Nm³ (straw) (dry flue gas at 13% O₂). Moreover, these results also provide first indications regarding the deposit formation risks associated with a certain biomass fuel. In addition, a good correlation between visually determined ash sintering tendencies and the sintering temperatures of the different fuels (according to ÖNORM CEN/TS 15370-1) could be observed. © 2013 American Chemical Society.

To examine relevant combustion characteristics of biomass fuels in grate combustion systems, a specially designed lab-scale reactor was developed. On the basis of tests performed with this reactor, information regarding the biomass decomposition behavior, the release of NO_x precursor species, the release of ash-forming elements, and first indications concerning ash melting can be evaluated. Within the scope of several projects, the lab-scale reactor system as well as the subsequent evaluation routines have been optimized and tests with a considerable number of different biomass fuels have been performed. These tests comprised a wide variation of different fuels, including conventional wood fuels (beech, spruce, and softwood pellets), bark, wood from short rotation coppice (SRC) (poplar and willow), waste wood, torrefied softwood, agricultural biomass (straw, Miscanthus, maize cobs, and grass pellets), and peat and sewage sludge. The results from the lab-scale reactor tests show that the thermal decomposition behavior and the combustion behavior of different biomass fuels vary considerably. With regard to NO_x precursors (NH₃, HCN, NO, N₂O, and NO₂), NH₃ and, for chemically untreated wood fuels, also HCN represent the dominant nitrogen species. The conversion rate from N in the fuel to N in NO_x precursors varies between 20 and 95% depending upon the fuel and generally decreases with an increasing N content of the fuel. These results gained from the lab-scale reactor tests can be used to derive NO_x precursor release models for subsequent computational fluid dynamics (CFD) NOx post-processing. The release of ash-forming vapors also considerably depends upon the fuel used. In general, more than 91% of Cl, more than 71% of S, 1–51% of K, and 1–50% of Na are released to the gas phase. From these data, the potential for aerosol emissions can be estimated, which varies between 18 mg/Nm³ (softwood pellets) and 320 mg/Nm³ (straw) (dry flue gas at 13% O2). Moreover, these results also provide first indications regarding the deposit formation risks associated with a certain biomass fuel. In addition, a good correlation between visually determined ash sintering tendencies and the sintering temperatures of the different fuels (according to ÖNORM CEN/TS 15370-1) could be observed.

In order to limit global warming to 1.5 °C compared to the pre-industrial temperature level, zero net CO2 emissions are needed on a global scale until 2050. A Chemical Looping (CL) process represents a technological system which is CO2-negative when using biomass as fuel and thus can substantially contribute to this target. In principle, the process uses a metal oxide as oxygen carrier material (OC) which is cyclically oxidized by air or steam and reduced by the fuel. Without air as the direct oxygen source for fuel conversion, high calorific product gases or pure carbon dioxide in case of combustion are obtained after the condensation of water vapor, which can then be stored or further utilized.
Within the funded project ”BIO-LOOP”, different Chemical Looping processes (for example combustion, gasification, hydrogen production) and reactors (fixed bed, fluidized bed) are investigated numerically and experimentally. An advanced process analysis tool based on mass and energy balances of the system considered will be presented. It provides data about the specific internal and external streams, process conditions and efficiencies. Within the analysis tool, various independent modular units describe individual process steps, e.g. mixing, chemical reaction or splitting. These components can be adjusted, combined and interconnected according to the flow chart of the system. The process model represents the first step towards a flexible Chemical Looping reactor simulation toolbox to analyze various process scenarios. Emphasis is put on the flexibility regarding the fuels and oxygen carriers, their conversion and possible process variations. The tool developed will support upcoming CFD modeling and further economic considerations.

Heterogeneous wastes, which cannot be material-recycled easily are used for energetic utilization. Certain quality criteria need to be met in this context, addressing especially the chlorine content due to the product quality as well as to environmental and safety issues. In regard of current issues in climate policy concerning emission trading, also an increased biogenic content in these waste fractions is desirable. Therefore, experiments with a sensor-based sorting technology at pilot scale as well as large scale have been conducted to analyse the technical feasibility of this technology for its application on heterogeneous wastes to gain products with desired material and quality criteria. The results of pilot scale experiments show that the sensor-based sorting technology is generally technically feasible to gain waste fractions with the required characteristics, if the technology was adjusted to the specific waste stream. Due to restrictions during the large scale experiment a number of further issues need to be addressed in
further experiments to allow for a concluding evaluation of that treatment concept.

The results of experimental work to investigate the effects of air staging on emissions from energy crop combustion in small scale applications are presented. Five different biomass fuels (wood, willow, miscanthus, tall fescue and cocksfoot) were combusted in a small scale (35 kW) biomass boiler and three different tests looking at the effects of (1) air ratio in the primary combustion chamber (primary air ratio), (2) temperature in the primary combustion chamber, and (3) overall excess air ratio, on NO_x and particulate emissions were conducted. It was shown that by varying the primary air ratio, NO_x emission reductions of between 15% (wood) and 30% (Miscanthus) and PM₁ reductions of between 16% (cocksfoot) and 26% (wood) were possible. For all fuels, both NO_x and particulate emissions were minimised at a primary air ratio of 0.8. Particulate emissions from miscanthus increased with increasing temperature in the primary combustion chamber, NO_x emissions from Miscanthus and from willow also increased with temperature. Overall excess air ratio has no effect on emissions as no significant differences were found for any of the fuels. Emissions of particulates and oxides of nitrogen from a wide range of biomass feedstocks can be minimised by optimising the primary air ratio and by maintaining a temperature in the primary combustion chamber of approximately 900 °C.

Direct ethanol fuel cells (DEFC) still lack active and efficient electrocatalysts for the alkaline ethanol oxidation reaction (EOR). In this work, a new instant reduction synthesis method was developed to prepare carbon supported ternary PdNiBi nanocatalysts with improved EOR activity. Synthesized catalysts were characterized with a variety of structural and compositional analysis techniques in order to correlate their morphology and surface chemistry with electrochemical performance. The modified instant reduction synthesis results in well-dispersed, spherical Pd85Ni10Bi5 nanoparticles on Vulcan XC72R support (Pd85Ni10Bi5/C(II-III)), with sizes ranging from 3.7 ± 0.8 to 4.7 ± 0.7 nm. On the other hand, the common instant reduction synthesis method leads to significantly agglomerated nanoparticles (Pd85Ni10Bi5/C(I)). EOR activity and stability of these three different carbon supported PdNiBi anode catalysts with a nominal atomic ratio of 85:10:5 were probed via cyclic voltammetry and chronoamperometry using the rotating disk electrode method. Pd85Ni10Bi5/C(II) showed the highest electrocatalytic activity (150 mA⋅cm−2; 2678 mA⋅mg−1) with low onset potential (0.207 V) for EOR in alkaline medium, as compared to a commercial Pd/C and to the other synthesized ternary nanocatalysts Pd85Ni10Bi5/C(I) and Pd85Ni10Bi5/C(III). This new synthesis approach provides a new avenue to developing efficient, carbon supported ternary nanocatalysts for future energy conversion devices.

n the course of this study the direct utilization of ammonia in different types of solid oxide fuel cells (SOFCs), such as anode- and electrolyte-supported SOFC, is investigated. Experiments in low fuel utilization, exhibited excellent performance of ammonia in SOFCs, although the power outputs of equivalent hydrogen/nitrogen fuels were not attained due to the incomplete endothermic ammonia decomposition. Next, the single cells were operated under high fuel utilization conditions and methane was added to the humidified ammonia stream, where they showed excellent ammonia- and methane conversions. The stability of the cells used was proven over a period of at least 48 hours with a variety of fuel mixtures. Post mortem scanning electron microscopy analysis of the anode micro-structures indicated nitriding effects of nickel, as microscopic pores and enlargements of the metallic parts occurred. Finally, a long-term test over 1,000 hours was carried out using a ten-layer stack consisting of electrolyte-supported cells.