The increasing demand for biomass fuels leads to the introduction of new biomass fuels into the market. These new biomass fuels (e.g., wastes and residues from agriculture and the food industry, short rotation coppices, and energy crops) are usually not well-defined regarding their combustion behavior. Therefore, fuel characterization methods with a special focus on combustion-related problems (gaseous NO x , HCl, and SO x emissions, ash-melting behavior, and PM emissions) have to be developed. For this purpose, fuel indexes are an interesting option. Fuel indexes are derived from chemical fuel analyses and are checked and evaluated regarding their applicability by measurements performed at lab-and real-scale combustion plants for a large variety of fuels. They provide the possibilities for a pre-evaluation of combustion-relevant problems that may arise from the use of a new biomass fuel. A possible relation to describe the corrosion risk is, for instance, the molar 2S/Cl ratio. The N content in the fuel is an indicator for NO x emissions, and the sum of the concentrations of K, Na, Zn, and Pb in the fuel can give a prediction of the aerosol emissions, whereas the molar (K + Na)/[x(2S + Cl)] ratio provides a first indication regarding the potential for gaseous HCl and SO x emissions. The molar Si/K ratio can supply information about the K release from the fuel to the gas phase. The molar Si/(Ca + Mg) ratio can give indications regarding the ash-melting temperatures for P-poor fuels. For Prich fuels, the (Si + P + K)/(Ca + Mg) ratio can be used for the same purpose. The fuel indexes mentioned can provide a first pre-evaluation of combustion-relevant properties of biomass fuels. Therefore, time-consuming and expensive combustion tests can partly be saved. The indexes mentioned are especially developed for grate combustion plants, because interactions of the bed material possible in fluidized-bed combustion systems are not considered.

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The interest in experimental data regarding thermal fuel decomposition as well as the release behavior of ash-forming elements of biomass fuels for modeling and simulation purposes is continuously increasing. On the basis of combustion experiments with lab-scale reactors and single-particle reactors, integral release data regarding ash-forming vapors can be obtained, whereby the release is calculated on the basis of analysis data of the fuel and the ash residues. At the moment, almost no time-resolved release data of ash-forming elements from single particles exist. Therefore, a single-particle reactor was designed, which has been coupled to an inductively coupled plasma mass spectrometer (ICP-MS). This reactor can be used for targeted experiments in a temperature range of 250–1050 °C under inert, reducing, and oxidizing conditions. With this reactor, it is possible to simultaneously determine the surface and center temperatures of a biomass particle, weight loss of the particle, and flue gas composition. The reactor has been coupled to an ICP-MS through a gas stream that is sufficiently diluted with Ar. First performance tests with pure salts (KCl, NaCl, (NH4)2SO4, ZnCl2, and PbCl2) proved that relevant volatile ash-forming elements can be detected with the ICP-MS. For a further validation of the received signals, combustion tests with Miscanthus pellets have been carried out, whereby the controlled interruption of the experiments has also been investigated. These tests prove that with this system the simultaneous time-resolved determination of S, Cl, K, Na, Zn, and Pb is possible whereby the Cl signal can only be used with restrictions. On the basis of the determined release of ash-forming elements for the entire combustion experiment, a quantification/calibration of the measured intensities has been carried out. The data gained from these tests will provide deeper insights into release processes as well as form a relevant basis for release model development.

The increased demand for energy from biomass enforces the utilization of new biomass fuels (e.g., energy crops, short-rotation coppices, as well as wastes and residues from agriculture and the food industry). Compared to conventional wood fuels, these new biomass fuels usually show considerably higher ash contents and lower ash sintering temperatures, which leads to increased problems concerning slagging, ash deposit formation, and particulate matter emissions. One possibility to combat these problematic behaviors is the application of fuel additives such as kaolin. In contrast to the usual approach for the application of additives based on an experimental determination of an appropriate additive ratio, this study applies novel and advanced fuel characterization tools for the characterization of biomass/kaolin mixtures. In the first step the pure biomass fuels (softwood from spruce and straw) and the additive were chemically analyzed. On the basis of the analysis theoretical mixing calculations of promising kaolin ratios were conducted. These theoretical mixtures were evaluated with fuel indexes and thermodynamic equilibrium calculations (TEC). Fuel indexes provide the first information regarding high temperature corrosion (2S/Cl) and ash melting tendency (Si + P + K)/(Ca + Mg + Al). TEC can be used for a qualitative prediction of the release of volatile and semivolatile elements (K, Na, S, Cl, Zn, Pb) and the ash melting behavior. Moreover, selected mixtures of spruce and straw with kaolin were prepared for an evaluation and validation of the release behavior of volatile and semivolatile ash forming elements with lab-scale reactor experiments. The validation of the ash melting behavior was conducted by applying the standard ash melting test. It could be shown that the new approach to apply novel and advanced fuel characterization tools to determine the optimum kaolin ratio for a certain biomass fuel works well and thus opens a new and targeted method for additive evaluation and application. In addition, it helps to significantly reduce time-consuming and expensive testing campaigns.

To gain better insight into inorganic element release processes, test runs with a specially designed single particle reactor connected with an inductively coupled plasma mass spectrometer (ICP-MS) have been performed. Relevant combustion related parameters such as mass loss during thermal degradation, temperature development of the particle (surface and center), and composition of released gases were recorded. By coupling the reactor to an ICP-MS, time-resolved release profiles of relevant aerosol forming elements (S, Cl, K, Na, Zn, and Pb) were determined. Targeted and controlled interruptions of the experiments (quenching) after a certain time were performed to validate reactor performance and reliability of the measurements. Test runs with softwood and straw pellets (8 mm in diameter and about 20 mm in length) were performed at reactor temperatures of 700, 850, and 1000 °C under oxidizing conditions (5.6 or 4.2 vol % O2). These test runs have revealed that the release ratios of volatile and semivolatile ash forming elements (S, Cl, K, Na, Zn, and Pb) generally increase as reactor temperatures rise. Moreover, regarding straw, higher Si and Al contents influence the release behavior of K, Na, Zn, and Pb. For K, existing release mechanisms proposed in the literature have been confirmed, and for Na it has been suggested that release mechanisms similar to K prevail. Especially during the starting phase of the experiment, a distinct temperature gradient exists from the surface to the center of the particle. Thus, different conversion phases occur in parallel in different layers of the particle, which has to be considered during the interpretation of the time-resolved release profiles of the main inorganic elements. Furthermore, transport limitations due to the occurrence of molten phases (especially for straw at reactor temperatures of 1000 °C) were obvious and could be directly derived from the online recorded release profiles. The targeted interruption of the ongoing decomposition process (quenching) provided an indication of the validity of the release profiles for S, K, Na, Zn, and Pb. Additionally, these experiments delivered valuable information regarding possible release mechanisms.