Fluidized bed combustion and gasification for phosphorus recovery by co-conversion of sewage sludge with biomass

Sammanfattning: In recent years, the thermal conversion of sewage sludge has proven its applicability for managing this inevitably generated waste. The viability arises from the concomitant features of recovering energy or valuable compounds, the breakdown of potentially harmful organic compounds, the separation or immobilization of heavy metals, and the formation of volume-reduced, sanitized residues. The inorganic residue after thermal conversion of municipal sewage sludge, i.e., the ash, is generally rich in phosphorus (P). Therein, P is mostly present in a chemical association that is poorly plant-available, e.g., apatite and whitlockite. Since sewage sludge ashes represent a P-rich resource, a number of different post-processing methods have been fathomed to extract P or alter its association in the ash. While extraction methods often focus on eluting P with acids, methods to alter the P-association in the ash rely mostly on thermochemical post-processing with additives. A way of enhancing the plant-availability of P in the ash is the thermochemical treatment with alkali additives, e.g., (Na,K)2SO4 and (Na,K)2CO3, leading to the formation of alkali-bearing phosphates of improved plant-availability. Providing the necessary physiochemical conditions for this phosphate alteration process, there is a potential to achieve the formation of alkali-bearing phosphates already during the thermal conversion of sewage sludge.This work investigates the potential of forming K-bearing phosphates in fluidized bed co-combustion and co-gasification processes of P-rich sewage sludge and K-rich agricultural residues. The focus was set on the fate and role of P in the interaction of the main ash-forming elements based on thermodynamic equilibrium studies, fundamental lab-scale investigations, and bench-scale fluidized bed experiments. Additionally, the benefits, e.g., fuel flexibility and high conversion rate, and ash-related risks due to interaction of ash and bed material when using fluidized bed systems are elaborated with a focus on bed material selection and investigating the operational modes of combustion and gasification.  The applicability of K- and Na-feldspar bed material in a pilot-scale indirect gasification system was investigated to provide a potential substitute for commonly used bed materials such as olivine and quartz. Olivine often contains heavy metals that could contaminate recovered ashes. Quartz may react with fuel-derived K, which could hamper the targeted formation of K-bearing phosphates and lead to bed material fragmentation and bed agglomeration. The bed material analysis of feldspar used in indirect wood gasification showed significant differences in the interaction phenomena between K- and Na-feldspar with the fuel ash. While both feldspar types displayed Ca-reaction and ash deposition layers on the particle surface, the interaction of Na-feldspar with K additionally led to the formation of K-reaction layers, possibly decreasing the bed particle integrity. The results suggest that K-feldspar is the preferred bed material option in terms of process stability and limiting the potential for side reactions of K when aiming for phosphate alteration towards K-bearing phosphates.Thermodynamic equilibrium calculations (TEC) were conducted with a focus on the fate of P and melting tendencies for a wide range of chemical compositions in biomass ashes and fuel mixtures between sewage sludge and the agricultural residues wheat straw (rich in Si and K) and sunflower husks (rich in K and Ca). The results for the K-Ca-Mg-P-Si-O system were validated with literature references, and an outline of practical implications was given. The results for sewage sludge and mixtures with agricultural residues functioned as a seminal tool for fuel design in practical investigations. The thermodynamic preference for forming alkali-bearing phosphates in competition with pure Ca-phosphates and incorporating K in silicates could be shown. The analysis of the K-Ca-Mg-P-Si-O system highlighted the influence of elemental ratios between and within the cation-formers (Mg, K, Ca) and the anion-formers (Si, P) on the fate of P and the ash melting tendency. The TEC for sewage sludge and mixtures with agricultural residues predicted that these elemental ratios are also the determining factors in the presence of large quantities of Al and Fe.Experimental research regarding the underlying ash chemistry with a focus on the fate of P was conducted in a single-pellet reactor and bench-scale fluidized bed combustion and gasification processes. The approach used sewage sludge pellets and co-pelletized mixtures with wheat straw and sunflower husks to determine the P-recovery potentials and potential operational risks. The parameters were chosen with relevance to practical applications of fluidized bed technologies. The experimental findings supported the TEC results in several aspects, such as the preference for Ca-phosphate formation in sewage sludge ash and the exclusion of Fe from the bulk ash matrix. However, the results also showed practical limitations for the formation of K-bearing phosphates in fuel mixture ashes. The identified limitations were the reaction of K with silicates in the fuel or the bed material, the high stability of Ca-rich orthophosphates, and the limited interaction of ash-forming elements in char residues from gasification processes. Additionally, the results from fluidized bed experiments highlighted the necessity for amendments in terms of fuel and bed material selection to avoid operational risks such as bed agglomeration.The results and discussions presented in this work allowed for the assessment of crucial process and fuel parameters for fluidized bed conversion systems using sewage sludge fuels and biomass fuel mixtures focusing on the formation of K-bearing phosphates. The importance of the ash transformation chemistry and its impact on selecting a suitable bed material could be outlined based on experimental and modeling data. The outcome shall assist the design of future large-scale applications in terms of a viable process and fuel design for energy and resource recovery from sewage sludge and agricultural residues.