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Phosphorus recovery from sewage sludge fluidized bed gasification processes
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Energy Science. (Energy Engineering)ORCID iD: 0000-0002-0488-438x
2020 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

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.

Place, publisher, year, edition, pages
Luleå: Luleå tekniska universitet, 2020.
Series
Licentiate thesis / Luleå University of Technology, ISSN 1402-1757
Keywords [en]
gasification, sewage sludge, agricultural residues, bed material, fluidized bed, feldspar, ash transformation, potassium, phosphorus, ICP-AES/MS, SEM, EDS, XRD, thermodynamic equilibrium modeling
National Category
Chemical Engineering Energy Engineering
Research subject
Energy Engineering
Identifiers
URN: urn:nbn:se:ltu:diva-81024ISBN: 978-91-7790-675-9 (print)ISBN: 978-91-7790-676-6 (electronic)OAI: oai:DiVA.org:ltu-81024DiVA, id: diva2:1474376
Presentation
2020-12-17, E632, E-huset, Luleå tekniska universitet, Luleå, 10:00 (English)
Opponent
Supervisors
Available from: 2020-10-08 Created: 2020-10-08 Last updated: 2025-02-18Bibliographically approved
List of papers
1. Layer Formation on Feldspar Bed Particles during Indirect Gasification of Wood. 1. K-Feldspar
Open this publication in new window or tab >>Layer Formation on Feldspar Bed Particles during Indirect Gasification of Wood. 1. K-Feldspar
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2019 (English)In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 33, no 8, p. 7321-7332Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
Dual Fluidized Bed, Bed Material, Wood, Feldspar
National Category
Chemical Engineering Energy Engineering
Research subject
Energy Engineering
Identifiers
urn:nbn:se:ltu:diva-75491 (URN)10.1021/acs.energyfuels.9b01291 (DOI)000481569100046 ()2-s2.0-85070922502 (Scopus ID)
Funder
Swedish Energy Agency, P46533-1 and P42034-1
Note

Validerad;2019;Nivå 2;2019-09-09 (johcin)

Available from: 2019-08-13 Created: 2019-08-13 Last updated: 2025-02-18Bibliographically approved
2. Layer Formation on Feldspar Bed Particles during Indirect Gasification of Wood. 2. Na-Feldspar
Open this publication in new window or tab >>Layer Formation on Feldspar Bed Particles during Indirect Gasification of Wood. 2. Na-Feldspar
Show others...
2019 (English)In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 33, no 8, p. 7333-7346Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
Dual Fluidized Bed, Bed Material, Wood, Feldspar
National Category
Energy Engineering
Research subject
Energy Engineering
Identifiers
urn:nbn:se:ltu:diva-75473 (URN)10.1021/acs.energyfuels.9b01292 (DOI)000481569100047 ()2-s2.0-85070917597 (Scopus ID)
Funder
Swedish Energy Agency, P46533-1 and P42034-1
Note

Validerad;2019;Nivå 2;2019-09-09 (johcin)

Available from: 2019-08-13 Created: 2019-08-13 Last updated: 2025-04-24Bibliographically approved
3. Thermochemical equilibrium study of ash transformation during combustion and gasification of sewage sludge mixtures with agricultural residues with focus on the phosphorus speciation
Open this publication in new window or tab >>Thermochemical equilibrium study of ash transformation during combustion and gasification of sewage sludge mixtures with agricultural residues with focus on the phosphorus speciation
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2021 (English)In: Biomass Conversion and Biorefinery, ISSN 2190-6815, E-ISSN 2190-6823, Vol. 11, no 1, p. 57-68Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
Springer, 2021
Keywords
Sewage sludge, Wheat straw, Sunflower husks, Modeling, Phosphorus recovery
National Category
Energy Engineering
Research subject
Energy Engineering
Identifiers
urn:nbn:se:ltu:diva-79370 (URN)10.1007/s13399-020-00772-4 (DOI)000537675600001 ()2-s2.0-85085986587 (Scopus ID)
Funder
Swedish Research Council Formas, 942-2015-619, 2017-01613Swedish Research Council, 2016-04380
Note

Validerad;2021;Nivå 2;2021-02-19 (alebob)

Available from: 2020-06-10 Created: 2020-06-10 Last updated: 2025-04-16Bibliographically approved

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