The necessity of recycling anthropogenically used phosphorus to prevent aquatic eutrophication and decrease the economic dependency on mined phosphate ores encouraged recent research to identify potential alternative resource pools. One of these resource pools is the ash derived from the thermochemical conversion of sewage sludge. This ash is rich in phosphorus, although most of it is chemically associated in a way where it is not plant available. The aim of this work was to identify the P recovery potential of ashes from sewage sludge co-conversion processes with two types of agricultural residues, namely wheat straw (rich in K and Si) and sunflower husks (rich in K), employing thermodynamic equilibrium calculations. The results indicate that both the melting behavior and the formation of plant available phosphates can be enhanced by using these fuel blends in comparison with pure sewage sludge. This enhanced bioavailability of phosphates was mostly due to the predicted formation of K-bearing phosphates in the mixtures instead of Ca/Fe/Al phosphates in the pure sewage sludge ash. According to the calculations, gasification conditions could increase the degree of slag formation and enhance the volatilization of K in comparison with combustion conditions. Furthermore, the possibility of precipitating phosphates from ash melts could be shown. It is emphasized that the results of this theoretical study represent an idealized system since in practice, non-equilibrium influences such as kinetic limitations and formation of amorphous structures may be significant. However, applicability of thermodynamic calculations in the prediction of molten and solid phases may still guide experimental research to investigate the actual phosphate formation in the future.

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Recycling of phosphorus in combination with increased utilization of bioenergy can mitigate material and global warming challenges. In addition, co-combustion of different fuels can alleviate ash-related problems in thermal conversion of biomass. The aim of this study is to investigate the ash transformation reactions of mainly P in co-combustion of P-rich sewage sludge (SS) with K-rich sunflower husks (SH) and K-and Si-rich wheat straw (WS). Single pellets of 4 mixtures (10 and 30 wt % SS in WS and 15 and 40 wt % SS in SH) and pure SS were combusted in an electrically heated furnace at process temperatures relevant for fluidized bed combustion (800 and 950 °C). Collected ash fractions were analyzed by inductively coupled plasma techniques, ion chromatography, scanning electron microscopy− energy-dispersive X-ray spectroscopy, and X-ray diffraction. Thermodynamic equilibrium calculations were performed to interpret the results. Over 90% of K and P was found to be captured within the residual ash with 30−70% P in crystalline K-bearing phosphates for mixtures with low amounts of SS (WSS10 and SHS15). The significant share of K and P in the amorphous material could be important for P recovery. For the lower percentage mixtures of SS (WSS10 and SHS15), P in crystalline phases was mainly found in K-whitlockite and CaKPO 4 . For the higher percentage SS mixtures, most of P was found in whitlockites associated with Fe and Mg, and no crystalline phosphates containing K were detected. For P recovery, co-combustion of the lower SS mixtures is favorable, and they are suggested to be further studied concerning the suitability for plant growth.

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.