One of the most sustainable pathways of sewage sludge treatment in recent years has been thermal conversion. The benefits of thermal treatment of sewage sludge are the recovery of energy or valuable chemical products, the destruction of harmful organic compounds, the separation of heavy metals from the P-rich coarse ash fraction, and the decreased and sanitized ash volume. The ashes created by these thermal conversion processes of sewage sludge are often rich in P that is mostly present in minerals with low plant-availability such as apatite. Due to the enrichment of P in the created ashes, a variety of post-processing steps have been developed to recover P from sewage sludge ashes. One proven way for the sus-tainable recovery of P from such ashes is thermal post-processing with alkaline salts, e.g., Na2SO4 or K2CO3, which was able to transform less plant-available phosphates in the sewage sludge into more plant-available alkali-bearing phos-phates. Based on these results, one could facilitate creating these phosphates with enhanced plant-availability by providing the chemical potential to form them already during the thermal conversion process of sewage sludge.  

This thesis aims to increase the current knowledge about the ash transformation processes of P and to suggest suitable process parameters for the alteration of the phosphate speciation in sewage sludge ashes by co-conversion with alkaline-rich agricultural residues. More specifically, the possibility of incorporating K derived from agricultural residues in phosphate structures derived from sewage sludge was evaluated with respect to the influence of the process temperature, the conver-sion atmosphere, and the fuel mixture. The studied parameters were chosen to generate knowledge relevant for fluidized bed gasification processes, with a spe-cial focus on dual fluidized bed (DFB) gasification systems.

The applicability of feldspar bed materials in fluidized bed gasification systems was investigated to enable the substitution of the commonly used olivine, which often contains heavy metals (potentially contaminating recovered ashes), and quartz, which is very reactive towards fuel-derived K and potentially leads to bed material fragmentation and bed agglomeration (Paper I & II). Subsequently, the thermodynamic potential for the alteration of the P-species in sewage sludge ash during co-combustion and co-gasification processes with agricultural residues was investigated (Paper III). Thereafter, an experimental evaluation of the ash transformation chemistry in thermal conversion processes of sewage sludge with different types of alkali-rich agricultural residues in temperatures relevant for flu-idized bed technology was conducted (Paper IV & V).

The methodology employed was chosen with respect to the state of technology of the specific investigated process. Paper I & II applied SEM, EDS, XRD, and thermodynamic equilibrium modeling for bed material samples derived from an industrial indirect gasifier. Paper III applied thermodynamic equilibrium calcula-tions to theoretically evaluate ash compositions resulting from co-conversion of sewage sludge and agricultural residues. Paper IV & V employed SEM, EDS, ICP-AES/MS, XRD, and thermochemical modeling on ash samples derived from single pellet lab-scale experiments.

The results obtained by analysis of bed material from indirect wood gasification showed the difference in interaction mechanism for K-feldspar and Na-feldspar, most notably the enhanced disintegration of Na-feldspar by K originating from the fuel (Paper I & II). Thermodynamic models employed for fuel mixtures of sewage sludge and agricultural residues showed the thermodynamic preference for the formation of the desired alkali-bearing phosphates (Paper III). Experi-ments conducted with these fuel mixtures (Paper IV & V) supported the theo-retical findings, and the influence of temperature and process conditions could be obtained. However, practical investigations also showed that attainment of the desired ash composition is subject to significant restrictions.

Derived from the elaborated results and discussions, it was possible to assess the critical process and fuel parameters for the development of up-scaled gasification processes focusing on the conversion of sewage sludge with the aim of creating improved phosphate formation in the ash. The selection of a suitable bed material in fluidized bed conversion and the transformation mechanisms defining the ash chemistry were found to be of vital importance for future applications. The pur-suit of the predefined aims in reference to P-recovery from sewage sludge has led to a multitude of suggestions for suitable process parameters that must be ad-dressed in future bench- and pilot-scale experimental runs.

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). However, P in sewage sludge ash 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, 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 toward 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 experimental 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 Lewis acid formers (Mg, K, Ca) and the Lewis base 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 of sewage sludge with wheat straw and sunflower husks to determine the P-recovery potentials and ash-related 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 Si, the high stability of Ca-rich orthophosphates, and the limited interaction of ash-forming elements in char residues from gasification processes. Furthermore, the results from the fluidized bed experiments highlighted the necessity for amendments in terms of fuel selection and fuel mixing to avoid operational risks such as bed agglomeration. The results of the conducted experimental investigations suggest that using K-feldspar as bed material in sewage sludge co-conversion setups with agricultural residues might benefit the incorporation of K in the P-rich ash fractions.

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.