Quartz, feldspar, and olivine are minerals commonly used as bed materials for dual fluidized bed gasification of biomass. During their interaction with biomass ash, the materials develop surface layers rich in ash-derived elements. These layers decrease the concentration of tar which is an unwanted side product of gasification. The interactions of quartz, feldspar, and olivine with woody biomass ash leading to the formation of active layers were studied with X-ray diffraction, scanning electron microscopy− energy dispersive X-ray spectroscopy, and iime-of-flight secondary ion mass spectrometry, and the results were compared to calculations done with FactSage. It was found that the interaction causes the formation of three-layered structures for all materials: a Mg-rich surface layer, a Ca-rich intermediate layer, and an inner layer which varies among the three materials. For quartz and feldspar, the integration of Ca and Mg into the structure causes a transition by depolymerizing the tectosilicate structure via an inosilicate intermediate to finally a nesosilicate. As the olivine structure is a nesosilicate from the beginning, no further depolymerization of the silicate structure can occur and a substitution of Mg by Ca occurs, leading to an accumulation of expelled MgO on the surface. The interaction of the materials with K was found to differ, causing melt formation for quartz, a substitution of Na-rich feldspar by K-rich feldspar, and the formation of feldspathoids for alkali feldspar, or retention as a separate phase for olivine.
The choice of bed material for biomass gasification plays a crucial role for the overall efficiency of the process. Olivine is the material conventionally used for biomass gasification due to the observed activity of olivine toward cracking of unwanted tars. Despite its catalytic activity, olivine contains high levels of chromium, which complicates the deposition of used bed material. Feldspar has shown the same activity as olivine when used as a bed material in biomass gasification. As opposed to olivine, feldspar does not contain environmentally hazardous compounds, which makes it a preferred alternative for further applications. The interaction of bed material and ash heavily influences the properties of the bed material. In the present study interactions between feldspar and main ash compounds of woody biomass in an indirect gasification system were investigated. Bed material samples were collected at different time intervals and analyzed with SEM-EDS and XRD. The obtained analysis results were then compared to thermodynamic models. The performed study was divided in two parts: in part 1 (the present paper), K-rich feldspar was investigated, whereas Na-rich feldspar is presented in part 2 of the study (DOI: 10.1021/acs.energyfuels.9b01291). From the material analysis performed, it can be seen that, as a result of the bed materials’ interactions with the formed ash compounds, the latter were first deposited on the surface of the K-feldspar particles and later resulted in the formation of Ca- and Mg-rich layers. The Ca enriched in the layers further reacted with the feldspar, which led to its diffusion into the particles and the formation of CaSiO3 and KAlSiO4. Contrary to Ca, Mg did not react with the feldspar and remained on the surface of the particles, where it was found as Mg- or Ca-Mg-silicates. As a result of the described interactions, layer separation was noted after 51 h with an outer Mg-rich layer and an inner Ca-rich layer. Due to the development of the Ca- and Mg-rich layers and the bed material–ash interactions, crack formation was observed on the particles’ surfaces.
Selecting a suitable bed material for the thermochemical conversion of a specific feedstock in a fluidized bed system requires identification of the characteristics of potential bed materials. An essential part of these characteristics is the interaction of the bed material with feedstock ash in a fluidized bed, which leads to layer formation and morphology changes. For this purpose, the interaction of feldspar bed material with the main ash-forming elements in wood ash (Ca, K, Mg, Si) in an indirect gasification system was analyzed using SEM-EDS, XRD, and thermodynamic modeling. In part 1 of this work (DOI: 10.1021/acs.energyfuels.9b01291), the layer formation on K-feldspar dominated by Ca reaction and ash deposition was investigated. The aim of this second part of the work was to determine the time-dependent layer formation on Na-feldspar and compare the results with the findings for K-feldspar. Interaction of Na-feldspar with ash-derived elements resulted in different layers on Na-feldspar: K reaction layers, where K replaced Na and Si shares decreased; Ca reaction layers, where Ca enriched and reacted with the Na-feldspar; and ash deposition layers, where wood ash elements accumulated on the surface. Ca reaction layers were formed first and became continuous on the surface before K reaction layers and ash deposition layers were detected. Cracks and crack layer formation in the Na-feldspar particles were found after several days of operation. The layer compositions and growth rates indicate that the diffusion of Ca and K plays an essential role in the formation of Ca reaction and K reaction layers. The reaction with Ca and the crack formation coincide with the interaction previously found for quartz and K-feldspar. In contrast to K-feldspar, Na-feldspar showed high potential for reaction with K. The findings indicate that the reaction of Na-feldspar with ash-derived K makes Na-feldspar a less stable bed material than K-feldspar during the thermochemical conversion of K-rich feedstocks in a fluidized bed system.
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