A great potential exists for increasing the use of bioenergy in thermochemical processes by utilizing agricultural biomass, forest residues, and sewage sludge that have high availability. Many of these biomass assortments have high ash contents with relatively high concentrations of ash-forming elements such as potassium (K), calcium (Ca), silicon (Si), and phosphorus (P). These elements can, during thermal conversion, cause several ash-related problems, such as deposit formation, slagging, and particle emissions. In particular, P has been found to play a vital role in such ash-related problems even at relatively low concentrations. In addition, ashes obtained from these biomass assortments could be an important source of valuable elements such as P and K. Therefore, detailed knowledge about the ash transformation and fate of P during thermal conversion of these opportunity biomass resources is of immense importance to mitigate ash-related problems and to recover valuable nutrient elements from the ash. 

The overall objective of this work was to determine the ash transformation and fate of P during single-pellet and fixed-bed combustion/gasification of different opportunity biomass fuels in the process temperature range of 600-1250°C. Different agricultural biomasses (poplar, wheat straw, grass, and wheat grain residues), forest residues (bark and twigs), and sewage sludge (pure and in mixtures with agricultural residues) were used. These fuels cover a wide range of overall ash compositions and different chemical associations of P in the fuel. The bark and poplar represent fuels rich in K and Ca with minor P content. The wheat straw, grass, and twigs represent typical Si- and K-rich fuels with minor to moderate P contents. The wheat grain residues (WGR) represent typical K- and P-rich fuels with a significant amount of Mg. The produced residual materials, i.e., char, different ash fractions and fine flue gas particles, were morphologically and chemically characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, inductively coupled plasma, and ion chromatography. The interpretation of the results was supported by thermodynamic equilibrium calculations.  

For all fuels, a major part of the P (> 80%) was found in coarse ash fractions because the studied process conditions favored the formation of stable condensed phosphates. The thermal conversion atmosphere (i.e., gasification/combustion) only caused small effects on the P release and the speciation of the P-compounds formed. Ash transformation pathways generally lead to the formation of orthophosphates (PO₄^3-) such as Ca₅(PO₄)₃(OH), CaKPO₄, and Ca₃(PO₄)₂ with the partial substitution of Ca by some cation forming elements (Fe, Mg, and/or K), as the main P containing crystalline phases. Crystalline pyrophosphate (P₂O₇^4-) compounds were also found in the residual ashes from the seed-based fuel (WGR), where P originates from phytate in the biomass. For the fuels containing a certain (sufficient) amount of Si, orthophosphates interact with silicate phases to form both amorphous and crystalline phosphosilicates. For the sewage sludge mixtures, a surplus of available K was needed to form K-bearing phosphates due to side reactions of K with Si and Al.  

The chemical form of P in the formed ash residues is thus strongly dependent on both the type of P association in the fuel and the relative concentrations of other major ash-forming elements, such as K, Ca, Si, and Al. For the fuels with a high (Ca+Mg)/P molar ratio (AER), i.e., for the typical wood-derived fuels bark and poplar, hydroxyapatite was the main P-containing crystalline phase found in the ash. For the studied fuels/fuel mixtures with moderate AER and a high (K+Na)/(Si+Al) molar ratio (AR), e.g., twigs, grass, wheat straw, and sewage sludge with high mixtures of agricultural residues, there was also a possibility to form alkali-bearing phosphates such CaKPO₄ and K-Mg whitlockite, besides hydroxyapatite. Since these fuels contain a high amount of Si, the P can be found in both amorphous phases, i.e. phosphosilicate, and Si substituted crystalline phases, i.e. Ca₁₀(SiO₄)_x(PO₄)_6-XOH_2-x and Ca₁₅(PO₄)₂(SiO₄)₆. For fuels with moderate AER and low AR, e.g., pure sewage sludge and sewage sludge with low mixtures of agricultural residues, K-bearing phosphates were not formed. Instead, P was found in phases such as whitlockite and phosphosilicates. For the WGR fuel with relatively low AER and high AR, K-bearing phosphates were formed in the ashes, where the P was found in crystalline K-Mg/Ca pyrophosphates and K-Mg orthophosphate, as well as amorphous K-Mg-Ca phosphates. 

The produced knowledge can potentially be used to, e.g., i) suggest efficient measures to mitigate ash-related problems associated with P during thermochemical conversion of opportunity biomass fuels, ii) suggest potential pathways to form plant-available phosphates directly in the thermal conversion process to enable recovery of P and K from the obtained ashes, and iii) find optimal thermal conversion process conditions to obtain bio charcoals that are suitable as alternative fuels and reducing agents in the metallurgical industry. 

The combustion of phosphorus (P)-rich biomass has a significant potential to increase the stock of biomass resources available for renewable heat and power production. In addition, the P-rich ashes have the potential as a fertilizer and could reduce the need for non-renewable P resources in agriculture. However, several technical challenges must be resolved to realize this potential.

During combustion, the ash-forming matter in the fuel undergoes numerous chemical transformations, which can result in the formation of ash melts. Excessive melt formation can lead to durable ash deposits in and around the combustion zone and on heat exchangers, which can lower combustion performance and, in severe cases, lead to a complete shutdown of the process. Further, mono-combustion of P-rich residues such as sewage sludge results in the formation of phosphates with poor plant availability, which can significantly limit the value of the ash as a fertilizer. By co-combustion the sludge with K-rich biomass, it may be possible to alter the chemical speciation of P towards more plant-available phases while simultaneously managing the risk of ash-related operational issues. This work investigates the effect of combustion technology, fuel ash composition, and chemical association of P in the fuel on the fate, i.e., distribution and speciation, and ash transformations of P in combustion and co-combustion of biomass and sewage sludge.

The basis of the study was experiments performed in three different combustion technologies, including a fluidized bed (5 kW, 730-800 °C), a fixed bed (20 kW, 950-1250 °C), and a powder burner (150 kW, ~1100°C). The fuels and fuel mixtures included P-rich and P-poor woody biomass, agricultural residues, and sewage sludge, which constitute a wide range of ash compositions in terms of K, Ca, Mg, Fe, Al, Si, and P. The residual ashes from the experiments were collected and chemically characterized with the original fuels and fuel mixtures to determine the ash transformation reactions of P. The experiments were complemented by thermodynamic equilibrium calculations (TECs), which aided the interpretation of experimental data and predicted the risk for operational issues related to the melting of coarse ash fractions.

The major share of fuel P was found in coarse ash fractions such as bed ash particles, bottom ash, slag, cyclone ash, wind side deposits, and coarse fly ash. A low share of fuel P was found in fine ash fractions such as leeside deposits and PM1. This generally matched the predictions by TEC, which indicated that P was stable in condensed phases at the relevant compositions and conditions during the combustion experiments. The powder burner experiments produced the highest share of fuel P in PM1 (4-14 wt.%), followed by fixed bed combustion (<4 wt.%), with fluidized bed combustion having the lowest share (<0.6 wt.%). In addition, the experiments with sewage sludge indicated a significantly lower P share in PM1 for a given combustion technology than the other biomass fuels, ranging from <0.2 wt.% in the fluidized bed and <1.2 wt.% in the fixed bed.

Combustion and co-combustion of woody biomass and agricultural residues resulted in the formation of a wide range of ortho-, pyro-, and metaphosphates associated with K, Ca, and Mg. Combustion of woody biomass generally resulted in a high share of Ca-orthophosphates, whereas agricultural residues had a higher share of K-rich ortho- and pyrophosphates. Irrespective of biomass assortment, the speciation of P in the ash from combustion and co-combustion followed general trends with respect to the fuel ash composition of the biomass mixture. The frequency and share of pyro- and metaphosphates identified in the coarse ash fractions tended to increase with the relative concentration of P to K, Ca, and Mg in the fuel mixture. A similar correlation was found between the share of K-rich phosphates and the relative concentration of K to Ca and Mg.

The crystalline phosphate phases identified in the coarse ash fractions from sewage sludge and K-rich biomass experiments were mainly Fe-rich and Ca-rich orthophosphate. The frequency and share of Fe-rich orthophosphates decreased with the relative P to K, Ca, and Mg concentration in the fuel mixture. However, the sewage sludge mixtures were less prone to form K-rich orthophosphates than the biomass mixtures for a given composition in terms of P to K, Ca, and Mg.

Based on TECs, it was possible to qualitatively predict ash-related issues related to the melting behavior of coarse ash fractions, such as slag formation, for woody biomass and agricultural residues by considering the K, Ca, Mg, Si, and P content in the fuel. The share of network formers (SiO2, PO2.5) to total ash oxides had the largest overall influence on the melting tendency of the ash mixture, followed by the ratio of K2O to total network modifiers (K2O, CaO, MgO), which had a high impact on ash mixtures with high relative shares of SiO2. The slagging tendency of fuel mixtures with a high share of sewage sludge could not be predicted based on the melting behavior of the K-Ca-Mg-Si-P-O system due to the high relative share of Fe and Al. The experimental results indicated that the slagging tendency of the sewage sludge was significantly improved by co-combustion with moderate amounts of wheat straw or sunflower husk.

Based on the combined results, it was possible to establish four fuel ash molar ratios correlated with the speciation of P in the produced coarse ash fractions and the risk of slag formation in fixed-bed combustion. These ratios were used to recommend practical fuel mixing strategies that could enable the production of combustion ashes with high P-plant availability while simultaneously managing the risk of severe slag formation.