| 1. |
- Hannl, Thomas Karl, M.Sc. 1993-
(författare)
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Phosphorus recovery from sewage sludge fluidized bed gasification processes
- 2020
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 2. |
- Hedayati, Ali, 1984-
(författare)
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Ash transformation in single-pellet combustion and gasification of biomass with special focus on phosphorus
- 2020
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The utilization of different biomass feedstocks in thermal conversion systems can contribute towards mitigation of global warming. However, the formation of different ash fractions (i.e., bottom ash, and fly ash) during thermal conversionof biomass can cause several ash-related problems such as deposit formation, slagging, and particle emissions, all of which may limit its usage as an energy source. It has been found that phosphorus (P), even in relatively low concentrations, can play a vitalrole in the abovementioned ash-related problems. However, the ash transformation reactions occurring in the thermal conversion of P-bearing biomass assortments are not fully understood and rarely described in the literature. Therefore, an understanding ofthe phenomena associated with ash transformations with a special focus on P is crucial.The overall objective was to determine the ash transformation and release of P duringsingle-pelletthermochemical conversion ofdifferent types of agricultural and forest fuelsin the low to medium temperature range (600-950 °C). Different agricultural biomasses (poplar, wheat straw, grass, and wheat grain residues), as well as forest residues (bark, twigs, and a mixture of bark and twigs) were used. Thebark and poplar fuels represent a fuel rich in K and Ca with minor P contents. The wheat straw, grass, and twigs represent a typical Si- and K-rich fuel with minor and moderate P contents. The wheat grain residues represent a typical K- and P-rich fuel witha considerable amount of Mg. The produced residual materials, i.e. chars and ashes, were characterized by SEM-EDS, XRD, and ICP-OES. The experimental results were interpreted with support from thermodynamic equilibrium calculations (TECs).The overall findings are that the majority of P (>80%) in all the studied fuels remained in the final condensed residues, and that the main fraction of P release occurred during the devolatilization stage. The chemical form of P in the residuesis strongly dependent on the relative concentrations of other major ash-forming elements such as K, Ca, and Si, as well as the type of association of P in the pure fuel. For woody-based fuels rich in Ca and K (poplar, bark, and twigs in this study), P in theash is generally found in the form of crystalline hydroxyapatite. For herbaceous fuels rich in Si and K (wheat straw and grass), P in the ash is generally found in Ca5(PO4)3OH, Ca15(PO4)2(SiO4),KCaPO4, and K-Ca/Mg phosphosilicate melts. For wheat grain residues rich in P, K, and Mg, P in the ash is found in crystalline forms K4Mg4(P2O7)3, K2MgP2O7,K2CaP2O7, and KMgPO4, as well as amorphous K-Mg/Ca phosphates.The obtained new knowledge can be used to find practical measures to mitigate ash-related problems during thermochemical conversion of P-bearing biomass fuels. It can also be used to find optimal pyrolysis process conditions to obtain biocharsuitable as alternative fuels and reducing agents in the metallurgical industry.
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| 3. |
- Häggström, Gustav
(författare)
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Experimental studies of ash transformation processes in thermochemical conversion of P-rich biomass and sludge
- 2020
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The efficient use of resources and sustainable recovery of various materials are important to minimize the anthropogenic impact on the climate and environment. One such resource is the phosphorus present in manure and sewage sludge. Various technologies are currently being developed to recover the phosphorus for the use of fertilizers in agricultural applications. Thermochemical conversion presents an opportunity to recover energy from these materials. At the same time, elements can be recovered in ash fractions, potentially harmful organic substances can be destroyed and heavy metals fractionated from the P. Mono-combustion of sewage sludge mainly produce apatite, which is not plant available and useful for fertilization. Co-combustion/-gasification with other fuels enables modification of ash transformation pathways and also remedy potential problems, such as bed agglomeration, associated with e.g. agricultural residues used as fuels. This thesis aims to increase the current knowledge in ash transformation of phosphorus-rich materials in cocombustion/-gasification with woody and agricultural fuels in process temperatures relevant for fluidized bed systems. The work focuses on i) possibility for formation of plant-available K-bearing phosphates ii) the effect of fuel ash composition and chemical association of P in the fuel on the distribution and speciation of P and iii) interaction of P-rich ash with bed material in fluidized beds. Experiments were carried out in bench-scale bubbling fluidized bed (BFB), macro-TGA (thermogravimetric analysis) combustion reactors and a dual fluidized bed (DFB) gasification reactor. Fuels studied were mixtures of chicken litter together with wheat straw and bark, and mixtures of digested sewage sludge combined with wheat straw and sunflower husk. Ash fraction and bed materials were collected and analyzed using ICP-OES/MS, SEM-EDS and XRD techniques. For the mixture of chicken litter and K- and Si-rich wheat straw, combusted in BFB, P and Si together with K and Ca formed homogeneous ash particles with large amounts of potentially amorphous iv content. A similar behavior was observed in sewage sludge and wheat straw mixtures where P and Si were likely present in a melt that is amorphous after extraction. In addition to these particles, P was also found in crystalline compounds such as hydroxyapatite, whitlockite and CaKPO4. For mixtures with Ca-rich bark, most of the phosphate formed was in the form of hydroxyapatite. In the interaction of ash with bed material, P captures Ca and K in phosphates, decreasing the interactions of these elements with the bed material, and thus can decrease the risk for bed agglomeration. The findings show that it is possible to modify the ash transformation of P towards K-bearing phosphates by co-combustion. Furthermore, they suggest that it is possible to recover most of the phosphorus in coarse ash fractions through co-combustion of P-rich materials with agricultural fuels. This means that P and volatile heavy metals can be separated into different ash fractions. This also increases the possibility of utilizing existing boilers for recovery of P as well as increased their flexibility to different fuels. To further validate the agricultural value of the produced ashes, plant growth studies have to be performed.
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