Development and Application of Devices for Online Trace Element Analysis of Thermal Process Gases from Woody Feedstocks

When using natural or waste wood in thermo-chemical conversion processes, the presence of a number of heteroatoms (e.g. sulfur, chlorine, potassium and sodium or heavy metals) may hinder the processes themselves as well as pose a threat to equipment and/or the environment. Due to the often strongly heterogeneous composition of the feedstocks and high dynamics of thermo-chemical reactions, the elemental concentrations in process gases show a high temporal variability. In order to accurately characterize such processes efficient and representative sampling methods and analytical instruments with a high sensitivity and time resolution are necessary. This thesis presents the development and application of devices to analyze trace element contents of product gases from thermo- chemical conversion processes and to characterize the thermal behavior of feedstocks such as wood pellets. In the first part the development of a mobile sampling and measurement system for the analysis of gaseous and liquid samples in the field is presented. An inductively coupled plasma optical emission spectrometer (ICP-OES) which was built into a van, was used as detector. The analytical system was calibrated with liquid and/or gaseous standards. It was shown that identical mass flows of either gaseous or liquid standards resulted in identical ICP-OES signal intensities. In a field measurement campaign trace and minor elements in the raw flue gas of a waste wood combustor were monitored. Sampling was performed with a highly transport efficient liquid quench system which made possible the observation of temporal variations in the elemental process gas composition. After a change in feedstock an immediate change of the element concentrations in the flue gas was detected. A comparison of the average element concentrations during the combustion of the two feedstocks showed a high reproducibility for matrix elements that are expected to be present in similar concentrations. Elements showing strong differences in their concentration in the feedstock were also represented by a higher concentration in the flue gas. Following the temporal variations of different elements revealed strong correlations between a number of elements, such as chlorine with sodium, potassium and zinc, as well as arsenic with lead, and calcium with strontium. Most notably, an online detector for alkalis (SID II) based on the principle of surface ionization has been designed and constructed within the framework this thesis. The detector includes a number of improvements compared to previous designs. Due to a fixed filament geometry, the sensitivity of the SID II is highly reproducible between different filaments. Improvements to the flow geometry of the device, and the installation of an auxiliary heateing element have minimized the overall tar depositions. In contrast to previous designs, the electrical feedthroughs are kept outside the sample gas stream and are therefore protected against tar contamination w