Für den ökonomisch und ökologisch effizienteren Betrieb von Dampfkesselanlagen ist die Untersuchung von Korrosionsvorgängen in Wärmetauschern, verursacht durch das Rauchgas aus einer Biomasse-Feuerung, notwendig. Daher wurden bei Bioenergy 2020+ kurzzeitige Korrosionsversuche im Umfang von 300h Betriebszeit an einem Wärmetauscherstahl 13CrMo4-5 mit einer ONLINE-Korrosionssonde der Firma Corrmoran GmbH für die Erstellung eines empirischen Korrosionsmodells durchgeführt. Als Brennstoffe dienten Waldhackgut, Weizenstrohpellets und Altholz. Die Messung benötigt eine Ionen leitende Deckschicht, die sich erst am Beginn des Versuchs aufbaut. Aufgrund der fehlenden Deckschicht wird daher zu Beginn der Messung der Korrosionsleitwert unterschätzt. Daraus ergeben sich systematische Messfehler. Ziel dieser Arbeit war die Eruierung des Zusammenhanges zwischen Messfehler und Versuchszeit. Dabei stellten sich zwei systematische Messfehler als relevant heraus: •Die Abzehrrate ist zum Korrosionsleitwert proportional. Daher wird die Abzehrrate während der Eingangsphase der Messung unterschätzt. •Die Abzehrrate berechnet sich aus dem Korrosionsleitwert, multipliziert mit einem Kalibrierungsfaktor. Dabei ergibt sich der Kalibrierungsfaktor aus dem Verhältnis des gesamten korrosionsbedingten Materialverlustes über die gesamte Versuchsdauer, dividiert durch den über denselben Zeitraum integrierten Korrosionsleitwert. Aufgrund des zu Beginn unterschätzten Korrosionsleitwertes wird der Kalibrierungsfaktor und somit die Abzehrrate, berechnet aus dem reproduzierbaren Signal, überschätzt. Die Literaturrecherche zeigte, dass die Kinetik bei der Hochtemperaturkorrosion bei konstant gehaltenen korrosionsrelevanten Parametern einen linearen, parabolischen oder paralinearen Verlauf einnehmen kann. Die kleinstmögliche Abzehrrate und somit der kleinstmögliche Korrosionsleitwert zu Beginn der Messung ergibt sich bei der Annahme eines linearen Verlaufs, welcher die möglicherweise erhöhten Abzehrraten der Initialkorrosion nicht mitberücksichtigt. Aus dieser Annahme konnte der kleinstmögliche Korrekturfaktor cmin berechnet werden. Dazu mussten die Daten bei konstant gehaltenen Parametern gefiltert und daraus der zeitlich integrierte Korrosionsleitwert PL,Messung gebildet werden. Das Verhältnis von PL,Messung mit einem über die gesamte Versuchszeit konstant angenommenen zeitlich integrierten Korrosionsleitwertes PL,linear ergibt den Korrekturfaktor, der multipliziert mit den ursprünglich bei gleichen Parametern bestimmten Abzehrraten eine neue Abzehrrate k(t)neu ergibt. Der Vergleich mit den Ergebnissen eines Langzeitversuches unter ähnlichen Betriebsbedingungen in einem Biomasse-Heizkraftwerk zeigte dadurch eine Verbesserung der Abweichung der Kurzzeitversuche von 125% auf 55%. Aufgrund der Parametervariationen sowie der Temperaturschwankungen, verursacht durch Ein- und Ausschaltvorgänge der Anlage, haben die bei konstanten Parametern bestimmten Korrekturfaktoren für die durchgeführten Versuche nur bedingt Gültigkeit. Daher wurde in einem weiteren Schritt ein Korrekturfaktor cmin,var bestimmt, welcher alle Daten der Versuchsserie berücksichtigt. Dazu wurde das Signal der Eingangsphase durch ein gleichlanges reproduzierbares Signal, gemessen unter denselben Bedingungen am Ende der Versuchsserien, ersetzt. Es ergibt sich aus dem Verhältnis der zeitlich integrierten Korrosionsleitwerte PL,Messung der Originalkurve zu PL,idealisiert des idealisierten Verlaufs der Korrekturfaktor cmin,var. Dieser hat aufgrund der Berücksichtigung aller gesammelten Daten für alle bei den Versuchen bestimmten Abzehrraten Gültigkeit. Durch cmin,var konnte eine Reduktion der Abweichung auf 110% erreicht werden. Diese wird auf die im Gegensatz zur Langzeitmessung im Biomasse-Heizkraftwerk unterschiedliche Versuchsmethode sowie auf den unbekannten Einfluss der möglicherweise erhöhten Abzehrraten der Initialkorrosion zurückgeführt.  

This study focuses on the determination of alkali release from wood and straw pellets during combustion. The aim is to expand the knowledge on the K and Na release behaviour and to adopt chemiluminescence-based sensors for online monitoring of alkali detection which can be applied for the prevention of fouling formation in low quality biomass combustion plants. Flame emission spectrometry (FES) was used for optical detection of chemiluminescence spectra of K and Na using optical bandpass filters mounted on an ICCD (Intensified Charge Coupled Device) camera. FES data were verified by additional experiments with a single particle reactor (SPR) coupled with an inductively coupled plasma mass spectrometer (ICP-MS). Using both techniques, the release profiles of K and Na during a single pellet combustion at 1000 °C were determined and obtained K* and Na* emission intensities directly correlated with the results from the ICP-MS. It was determined that the emission intensity of alkali radicals depends on alkali concentrations in the samples and K and Na radical emission intensities increase with increasing alkali amounts in the samples. The ICP-MS data revealed that the release of K and Na mainly takes place during the stage of devolatilization. During devolatilization, almost all potassium and sodium are released from wood samples, while only 65–90% of K and 74–90% of Na are released from straw samples. Based on the results, the flame emission spectroscopy technique is capable to fully detect released alkali metals in the gas phase during combustion and proves a possibility to use flame emission sensors for monitoring the release of alkali species from biomass during combustion processes.

During transportation and storage of wood pellets various gases are formed leading to toxic atmosphere. Various influencing factors and measures reducing off-gassing have already been investigated. The present study aims at applying an antioxidant, acetylsalicylic acid (ASA), to reduce off-gassing from wood pellets by lowering wood extractives oxidation. Therefore, acetylsalicylic acid was applied in industrial and laboratory pelletizing processes. Pine and spruce sawdust (ratio 1:1) were pelletized with adding 0-0.8% (m/m) ASA. Glass flasks measurements confirmed off-gassing reduction by adding ASA for all wood pellets investigated.The biggest effect was achieved by adding 0.8% (m/m) ASA in the industrial pelletizing experiments where the emission of volatile organic compounds (VOC_tot) was reduced by 82% and a reduction of carbon monoxide (CO) and carbon dioxide (CO₂) emissions by 70% and 51%, respectively, could be achieved. Even an addition of 0.05% (m/m) ASA led to off-gassing reduction by >10%. A six week storage experiment to investigate the long-term effectivity of ASA addition revealed, that antioxidant addition was effective in reducing CO-, CO₂- and VOC_tot-release, especially during the first four weeks of the storage experiment, after which time the relative reduction effect was significantly decreased.

In this study, we investigated the emissions, including odor, from log wood stoves, burning wood types indigenous to mid-European countries such as Austria, Czech Republic, Hungary, Slovak Republic, Slovenia, Switzerland, as well as Baden-Württemberg and Bavaria (Germany) and South Tyrol (Italy). The investigations were performed with a modern, certified, 8 kW, manually fired log wood stove, and the results were compared to emissions from a modern 9 kW pellet stove. The examined wood types were deciduous species: black locust, black poplar, European hornbeam, European beech, pedunculate oak (also known as “common oak”), sessile oak, turkey oak and conifers: Austrian black pine, European larch, Norway spruce, Scots pine, silver fir, as well as hardwood briquettes. In addition, “garden biomass” such as pine cones, pine needles and dry leaves were burnt in the log wood stove. The pellet stove was fired with softwood pellets.

The composite average emission rates for log wood and briquettes were 2030 mg MJ⁻¹ for CO; 89 mg MJ⁻¹ for NO_x, 311 mg MJ⁻¹ for C_xH_y, 67 mg MJ⁻¹ for particulate matter PM₁₀ and average odor concentration was at 2430 OU m⁻³. CO, C_xH_y and PM₁₀ emissions from pellets combustion were lower by factors of 10, 13 and 3, while considering NO_x – comparable to the log wood emissions. Odor from pellets combustion was not detectable. CxHy and PM10 emissions from garden biomass (needles and leaves) burning were 10 times higher than for log wood, while CO and NO_x rise only slightly. Odor levels ranged from not detectable (pellets) to around 19,000 OU m⁻³ (dry leaves). The odor concentration correlated with CO, C_xH_y and PM₁₀. For log wood combustion average odor ranged from 536 OU m⁻³ for hornbeam to 5217 OU m⁻³ for fir, indicating a considerable influence of the wood type on odor concentration.

The increased biomass utilization leads to the need of an efficient and flexible usage of available sources. Therefore, it is necessary to combust low-cost biogenic residues, which inherently have higher nitrogen contents that lead to increased NOx emissions. In order to tackle this issue a new combustion technology with double air staging and flue gas recirculation is under development. The technology also features an increased fuel bed height and very low oxygen concentrations in the fuel bed to reduce fuel bed temperatures. This work focuses on the CFD simulation of the formation and reduction of NOx emissions of in a small scale boiler (35 kWth). Compared to previously applied models, major modification concerning the heat and mass transfer in the fuel bed as well as the subsequent conversion in the freeboard were made. The fuel bed is modelled via representative fuel particles with a Lagrangian approach and a thermally thick particle model considering intra-particle
gradients. Due to the increased fuel bed height and the relatively low oxygen concentration the formation and cracking of tars has to be considered in the simulation. This heavily influences the formation and reduction of NOx and its precursors. The fuel bound nitrogen is released via the particle model in the form of NO during char burnout and via a lumped tar species during pyrolysis. The cracking of the lumped tar species is modelled via two global gas phase reactions that releases the NOx precursors NH3 and HCN. The cracking reactions are added to a skeletal reaction mechanism with 28 species and 102 reactions that includes the fate of the N species. The simulation results are compared to experimental data from test runs with spruce wood chips and Miscanthus pellets as fuels. The comparison showed good agreement for the test runs with wood chips, where the temperature distribution inside the fuel bed and the released species above the fuel bed were predicted well. The test runs with Miscanthus showed a greater deviation between the measured and simulated values. For both fuels the NOx reduction that was experimentally observed in the secondary combustion zone could not be predicted with reasonable agreement. Therefore, it is necessary to further investigate the cracking of the tars and the subsequent formation of the NOx precursors. The presented work forms the basis for further improvements of the numerical models and subsequently the optimization of the new technology.

A method for deriving kinetic models of gas–solid reactions for reactor and process design is presented. It is based on the nonparametric kinetics (NPK) method and resolves many of its shortcomings by applying tensor rank‐1 approximation methods. With this method, it is possible to derive kinetic models based on the general kinetic equation from any combination of experiments without additional a priori assumptions. The most notable improvements over the original method are that it is computationally much simpler and that it is not limited to two variables. Two algorithms for computing the rank‐1 approximation as well as a tailored initialization method are presented, and their performance is assessed. Formulae for the variance estimation of the solution values are derived to improve the accuracy of the model identification and to provide a tool for diagnosing the quality of the kinetic model. The methods effectiveness and performance are assessed by applying it to a simulated data set. A Matlab implementation is available as Supporting Information.

Pellet boilers and pellet stoves are widely used for heat production. But in most cases, only specific wood pellets with a low ash content are approved due to the increased risk of slagging and limited deashing capacity. The ash fusion test (AFT), according to prCEN/TS 15370-1, is currently the only standard method for the prediction of slagging. This method is not feasible for all biomass fuel types, since sometimes the characteristic temperatures cannot be determined or the characteristic shapes do not occur for temperature determination. Furthermore, the method is costly and requires complex instrumental infrastructure. Hence, a demand for more expressive or more rapid methods to characterize slag formation potential of fuels is often claimed. Based on a literature study, four such laboratory test methods were chosen, partly adapted, and then experimentally investigated. These methods included thermal treatment of the fuel itself or the ashes of the fuel and were the rapid slag test, CIEMAT, the slag analyzer, and the newly developed pellet ash and slag sieving assessment (PASSA) method. Method performance was practically assessed using 14 different biomass fuel pellets, which were mainly from different assortments of wood, but also herbaceous or other nonwoody fuels. The results from the tests with these four alternative methods were evaluated by comparing to both results from standard AFT and results from full-scale combustion tests performed over a maximum of 24 h. Seven different pellet boilers were assessed, of which one boiler was used to apply all 14 test fuels. According to the granulometric ash analysis (i.e., the ratio of >1 mm-fraction toward total ash formed), the sensitivity of the new test methods to depict slagging phenomena at a suitable level of differentiation was assessed. Satisfactory conformity of the boiler ash assessment (reference) was found for both, the slag analyzer and the PASSA method. The latter may, in particular, be seen as a promising and relatively simple low-input procedure, which can provide more real-life oriented test results for fixed-bed combustion. The standardized AFT could, however, not sufficiently predict the degree of slag actually formed in the reference boiler, particularly when only wood fuels are regarded.

Holzpellets werden in zunehmendem Maße aus Hackschnitzel hergestellt. Es ist davon auszugehen, dass diese Veränderung der Rohstoffbasis zu erhöhten Aschegehalten im Brennstoff führt und zu Schwierigkeiten bei der Nutzung führen kann. Die vorliegende Arbeit kommt zum Schluss, dass moderate Anteile (< 5%) sauberer Rinde zu keinen wesentlichen Verschlackungen führen. Bei Verunreinigung oder / und sehr hohen Rindenanteilen ist mit
Verschlackungsproblemen jedenfalls zu rechnen.

The release of potassium during biomass combustion leads to several problems as the emissions of particle matter or formation of deposits. K release is mainly described in literature in a qualitative way and this work aims to develop a simplified model to quantitatively describe it at different stages. The proposed model has 4 reactions and 5 solid species, describing K release in 3 steps; during pyrolysis, KCl evaporation and carbonate dissociation. This release model is coupled into a single particle model and successfully validated with experiments conducted in a single particle reactor with spruce, straw and Miscanthus pellets at different temperatures. The model employs same kinetic parameters for the reactions in all cases, while different product compositions of the reactions are employed for each fuel, which is attributed to differences in composition. The proposed model correctly predicts the online release at different stages during conversion as well as the final release for each case.