| 1. |
- Hannl, Thomas Karl, M.Sc. 1993-, et al.
(författare)
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Ash transformation during single-pellet gasification of sewage sludge and mixtures with agricultural residues with a focus on phosphorus
- 2022
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Ingår i: Fuel processing technology. - : Elsevier. - 0378-3820 .- 1873-7188. ; 227
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Tidskriftsartikel (refereegranskat)abstract
- The recovery of phosphorus (P) from sewage sludge ashes has been the focus of recent research due to the initiatives for the use of biogenic resources and resource recovery. This study investigates the ash transformation chemistry of P in sewage sludge ash during the co-gasification with the K-Si- and K-rich agricultural residues wheat straw and sunflower husks, respectively, at temperatures relevant for fluidized bed technology, namely 800 °C and 950 °C. The residual ash was analyzed by ICPAES, SEM/EDS, and XRD, and the results were compared to results of thermochemical equilibrium calculations. More than 90% of P and K in the fuels were retained in the residual ash fraction, and significant interaction phenomena occurred between the P-rich sewage sludge and the K-rich ash fractions. Around 45–65% of P was incorporated in crystalline K-bearing phosphates, i.e., K-whitlockite and CaKPO4, in the residual ashes with 85–90 wt% agricultural residue in the fuel mixture. In residual ashes of sewage sludge and mixtures with 60–70 wt% agricultural residue, P was mainly found in Ca(Mg,Fe)-whitlockites and AlPO4. Up to about 40% of P was in amorphous or unidentified phases. The results show that gasification provides a potential for the formation of K-bearing phosphates similar to combustion processes.
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| 2. |
- 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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| 3. |
- Häggström, Gustav, et al.
(författare)
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Fate of Phosphorus in Fluidized Bed Cocombustion of Chicken Litter with Wheat Straw and Bark Residues
- 2020
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 0887-0624 .- 1520-5029. ; 34:2, s. 1822-1829
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Tidskriftsartikel (refereegranskat)abstract
- This study aims to determine the fate of P during fluidized bed co-combustion of chicken litter (CL) with K-rich fuels [e.g., wheat straw (WS)] and Ca-rich fuels (bark). The effect of fuel blending on phosphate speciation in ash was investigated. This was performed by chemical characterization of ash fractions to determine which phosphate compounds had formed and identify plausible ash transformation reactions for P. The ash fractions were produced in combustion experiments using CL and fuel blends with 30% CL and WS or bark (B) at 790–810 °C in a 5 kW laboratory-scale bubbling fluidized bed. Potassium feldspar was used as the bed material. Bed ash particles, cyclone ash, and particulate matter (PM) were collected and subjected to chemical analysis with scanning electron microscopy–energy-dispersive X-ray spectrometry (SEM–EDS) and X-ray diffraction. P was detected in coarse ash fractions only, that is, bed ash, cyclone ash, and coarse PM fraction (>1 μm); no P could be detected in the fine PM fraction (<1 μm). SEM–EDS analysis showed that P was mainly present in K–Ca–P-rich areas for pure CL as well as in the ashes from the fuel blends of CL with WS or B. In the WS blend, P was found together with Si in these areas. The crystalline compound containing P was hydroxyapatite in all cases as well as whitlockite in the cases of pure CL and WS blend, of which the latter compound has been previously identified as a promising plant nutrient. The ash fractions from CL and bark blend only contained P in hydroxyapatite. Co-combustion of CL together with WS appears to be promising for P recovery, and ashes with this composition could be further studied in plant growth experiments.
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| 4. |
- Häggström, Gustav, et al.
(författare)
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Fate of phosphorus in pulverized fuel co-combustion of sewage sludge and agricultural residues
- 2023
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Ingår i: Fuel. - : Elsevier. - 0016-2361 .- 1873-7153. ; 335
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Tidskriftsartikel (refereegranskat)abstract
- The fate of phosphorus concerning its distribution in the thermal process and chemical speciation was studied during the co-combustion of sewage sludge with wheat straw and sunflower husks in powder combustion conditions. Co-combustion experiments were performed in a lab-scale entrained flow reactor (EFR) at 1000 °C and 1400 °C. SEM-EDS and ICP-OES analyses were used for studies of deposits collected on a probe, bottom ash, and particulate matter samples collected during experiments. Deposition probe samples were further studied and interpreted using powder X-ray diffraction (XRD) and thermochemical equilibrium calculations (TECs). The inorganic material in the different fuel particles mainly interacted through a molten phase observed on deposition probes. Crystalline P was mainly identified in β-Ca3(PO4)2 whitlockites. TECs support the experimental findings and suggest that a mostly homogenous melt occurs at 1400 °C, whereas Fe-oxides and Ca-phosphates precipitate during the cooling of the formed deposits. It was found that <5 % of incoming P was collected in fine particulate matter (<1 µm), indicating that the majority of P can be found in deposits and bottom ash. This outcome implies that P recovery efforts should be focused on these ash fractions.
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| 5. |
- Häggström, Gustav, et al.
(författare)
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Single Pellet Combustion of Sewage Sludge and Agricultural Residues with a Focus on Phosphorus
- 2021
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 0887-0624 .- 1520-5029. ; 35:12, s. 10009-10022
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Tidskriftsartikel (refereegranskat)abstract
- Recycling of phosphorus in combination with increased utilization of bioenergy can mitigate material and global warming challenges. In addition, co-combustion of different fuels can alleviate ash-related problems in thermal conversion of biomass. The aim of this study is to investigate the ash transformation reactions of mainly P in co-combustion of P-rich sewage sludge (SS) with K-rich sunflower husks (SH) and K-And Si-rich wheat straw (WS). Single pellets of 4 mixtures (10 and 30 wt % SS in WS and 15 and 40 wt % SS in SH) and pure SS were combusted in an electrically heated furnace at process temperatures relevant for fluidized bed combustion (800 and 950 °C). Collected ash fractions were analyzed by inductively coupled plasma techniques, ion chromatography, scanning electron microscopy-energy-dispersive X-ray spectroscopy, and X-ray diffraction. Thermodynamic equilibrium calculations were performed to interpret the results. Over 90% of K and P was found to be captured within the residual ash with 30-70% P in crystalline K-bearing phosphates for mixtures with low amounts of SS (WSS10 and SHS15). The significant share of K and P in the amorphous material could be important for P recovery. For the lower percentage mixtures of SS (WSS10 and SHS15), P in crystalline phases was mainly found in K-whitlockite and CaKPO4. For the higher percentage SS mixtures, most of P was found in whitlockites associated with Fe and Mg, and no crystalline phosphates containing K were detected. For P recovery, co-combustion of the lower SS mixtures is favorable, and they are suggested to be further studied concerning the suitability for plant growth.
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| 6. |
- Häggström, Gustav
(författare)
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Studies of ash transformation processes in thermochemical co-conversion of phosphorus-rich manure and sludge with biomass residues
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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 (P) present in manure and sewage sludge. Various technologies are currently being developed to recover the element for application as fertilizer in agricultural applications. Thermochemical conversion presents the opportunity to recover energy from these materials. In a single process, 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, a phosphate mineral with low plant availability and therefore less useful for fertilization. Co-combustion/-gasification with other fuels enables modification of the ash transformation reaction pathways and remedies potential problems, such as bed agglomeration, associated with forestry and agricultural residues when used as fuels.The overall objective of this work was to increase the current knowledge in ash transformation of P-rich materials in co-conversion with forestry and agricultural residues in order to facilitate the P-recovery by formation of suitable phosphates in the ash. The work focuses on i) the influence of co-conversion on ash transformation of P with a focus on altering speciation of P towards the potentially more plant-available K-bearing phosphates ii) the influence of fuel ash composition and chemical association of P in the fuel, temperature and particle interaction on the fate, i.e. speciation and distribution, of P and iii) practical implications of co-conversion in fluidized bed and pulverized fuel systems for P-recovery, specifically interaction of P-rich ash with bed material in fluidized beds and strategies for extracting P-rich ashes.Experiments were carried out in a bench-scale bubbling fluidized bed reactor (BFB), macro-thermogravimetric analysis (TGA) conversion reactor, a dual fluidized bed (DFB) gasification reactor, and an entrained flow reactor (EFR) for pulverized fuel combustion. The 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. The process temperature ranges studied were 800-950 °C for BFB and single-pellet macro-TGA studies, whereas 1000 °Cand 1400 °C were investigated in pulverized fuel combustion studies using the EFR. Ash fractions and bed materials were collected and analyzed using scanning electron microscopy with energy-dispersive Xray spectroscopy (SEM-EDS), powder X-ray diffraction (XRD), inductively coupled plasma with atomic emission spectroscopy (ICPAES) and ion chromatography (IC). The results were interpreted with the support of thermodynamic equilibrium calculations (TECs) using FactSage software with the GTOX & SGPS databases.For all investigated conditions and fuel mixtures, the major part of P (> 90 %) was found in coarse ash fractions, suggesting that the recovery potential is highest in these fractions. This also means that P and volatile heavy metals can be separated in different ash fractions. Crystalline P was to a higher degree observed in the form of K-bearing whitlockite structures and CaKPO4 in mixtures containing low amounts of sewage sludge and high amounts of agricultural residues rich in K. K-bearing whitlockites were also found in ash of chicken litter and its mixture with wheat straw, as well as in ash deposits formed in pulverized combustion with a sewage sludge and wheat straw mixture combusted at 1000 °C. In mixtures with higher shares of sewage sludge, crystalline P was mainly found as Fe- and Mg-substituted whitlockites and hydroxyapatite. The reaction pathway of P appears to mainly occur through substitution and addition reactions in the condensed phase. The findings show that it is possible to modify the ash transformation of P towards K-bearing phosphates by co-conversion and that the difference between combustion and gasification is small.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 content. A similar behavior was observed in sewage sludge and wheat straw mixtures, where P and Si were likely present in a melt that was amorphous after extraction. In addition to these particles, P was also observed in crystalline orthophosphate compounds such as hydroxyapatite, aluminium phosphate, whitlockites and CaKPO4. In the mixture of chicken litter with Ca-rich bark, crystalline P was found in the form of hydroxyapatite. In fuel mixtures with higher amounts of Al with Si, the capture of K in aluminosilicates was higher, making it unavailable to form K-bearing phosphates. Small differences in the fate of P, between organically and inorganically associated P found in the fuels were seen in this work. Lower temperatures (800 °C compared to 950 °C) favored the formation of crystalline K-bearing phosphates in single-pellet combustion of sewage sludge and agricultural residues. In pulverized fuel combustion experiments, more crystalline K-bearing phosphates were found at 1000°C compared to 1400 °C. Fuel ash interaction mainly occurred in condensed phases in ash deposits compared to interactions between particles entrained in the flow.In fluidized bed experiments, P captured Ca and K in relatively high temperature melting phosphates in the fuel ash, decreasing the interactions of these elements with the bed material and thus decreased the risk for bed agglomeration. Possible extraction strategies involve the separation of coarse ash particles from bed material particles or in heated cyclones, avoiding fine ash fractions known to be rich in volatile heavy metals. Mixtures of coarse ash and bed material can potentially also be used for P-recovery. Co-conversion increases the possibility of utilizing existing boilers for recovery of P and increasing their flexibility to different fuels. The results indicate that a powder combustor operating in slagging mode could be a feasible strategy for P recovery because the interaction potential between the formed individual coarse ash particles increases at the hot wall. Plant growth studies have to be performed to further validate the agricultural value of the produced ashes for direct soil application.
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| 7. |
- Kirtania, Kawnish, et al.
(författare)
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Cogasification of Crude Glycerol and Black Liquor Blends: Char Morphology and Gasification Kinetics
- 2017
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Ingår i: Energy Technology. - : John Wiley & Sons. - 2194-4296 .- 2194-4288. ; 5:8, s. 1272-1281
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Tidskriftsartikel (refereegranskat)abstract
- This study assesses the feasibility of black liquor/glycerol blends as potential gasification feedstock. The char gasification reactivity and kinetics were studied at T = 750 °C, 800 °C, 850 °C and 900 °C for 20% and 40% blends of glycerol with black liquor. Three qualities of glycerol were used including two industrial grade crude glycerols. Gasification rates were similar for all blends, indicating sufficient alkali metal catalysis also for the char blends (Alkali/C atomic ratio between 0.45 and 0.55). The blends with the most impure glycerol (containing K) were found to have the lowest activation energies (~120 kJ/mol) and reaction times for char gasification indicating fuel properties suitable for gasification. Char particles from different blends showed similar surface morphology as black liquor chars with even surface distribution of alkali elements. A loss of alkali (mainly, K) from the fuel blends during pyrolysis indicated the necessity to perform gas-phase studies of alkali release. Overall, these results encourage the use of glycerol as a potential gasification feedstock for catalytic gasification based bio-refineries.
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| 8. |
- Nielsen, Ida, et al.
(författare)
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Water driven phase transitions in Prussian white cathode materials
- 2022
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Ingår i: Journal of Physics. - : Institute of Physics (IOP). - 2515-7655. ; 4:4
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Tidskriftsartikel (refereegranskat)abstract
- Prussian white (PW, Na2Fe [Fe(CN)(6)] center dot zH(2)O) is a promising cathode material for use in sodium-ion batteries for large-scale energy storage applications, which demand long cycling life-times. However, for non-aqueous battery applications PW must not contain any water, and yet dehydration induces a large volume change destabilizing the structure and reducing the cycling life. The material undergoes multiple phase transitions as a function of both the sodium and water content, however, the mechanism behind is poorly understood. Here, we use neutron diffraction to explore the influence of water on the structure of PW. For the first time, two structures for a single composition of PW were observed near room temperature independent of the synthesis method. These structures differ in the FeN6 and FeC6 octahedral tilting configurations, which is connected to the ordering of water in the framework. The removal of water modulates the magnitude of pre-existing structural distortions, if it is itself disordered within the structure, rather than modifying the nature of the distortions. These results provide a robust fundamental understanding of the chemical driving force impacting the nature and magnitude of structural distortions in Prussian blue analogues. The insights provide guidance for designing tilt-engineering ultimately enabling new materials with enhanced long-term electrochemical performance in battery applications.
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| 9. |
- Svensson, Marie, et al.
(författare)
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Control of endotoxin release in Escherichia coli fed-batch cultures
- 2005
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Ingår i: Bioprocess and biosystems engineering (Print). - : Springer Science and Business Media LLC. - 1615-7591 .- 1615-7605. ; 27:2, s. 91-97
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Tidskriftsartikel (refereegranskat)abstract
- High amounts of outer membrane (OM) components were released in glucose-limited fed-batch (GLFB) cultures at 37 degrees C at specific growth rates approaching 0.05 h(-1). Endotoxin analyses from a 20 degrees C GLFB culture gave similar results. An alternative fermentation technique, the temperature-limited fed-batch (TLFB) technique, reduced the endotoxin concentration in a culture with a biomass concentration of 30 g l(-1) from the 850 mg l(-1) in traditional GLFB cultures to about 20 mg l(-1). The TLFB technique uses the temperature to regulate the dissolved oxygen tension, while all substrate components are unregulated. It appears to be severe glucose limitation that triggers the extensive release of endotoxins rather than a low growth rate. Furthermore, it is not the low temperature that stabilizes the OM when using the TLFB technique. Simulations and experimental data show that this technique results in the same biomass productivity as the GLFB technique.
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| 10. |
- Umeki, Kentaro, et al.
(författare)
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Reduction of tar and soot formation from entrained-flow gasification of woody biomass by alkali impregnation
- 2017
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 0887-0624 .- 1520-5029. ; 31:5, s. 5104-5110
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Tidskriftsartikel (refereegranskat)abstract
- Tar and soot in product gas have been a major technical challenge toward the large-scale industrial installation of biomass gasification. This study aims at demonstrating that the formation of tar and soot can be reduced simultaneously using the catalytic activity of alkali metal species. Pine sawdust was impregnated with aqueous K2CO3 solution by wet impregnation methods prior to the gasification experiments. Raw and alkali-impregnated sawdust were gasified in a laminar drop-tube furnace at 900–1400 °C in a N2–CO2 mixture, because that creates conditions representative for an entrained-flow gasification process. At 900–1100 °C, char, soot and tar decreased with the temperature rise for both raw and alkali-impregnated sawdust. The change in tar and soot yields indicated that potassium inhibited the growth of polycyclic aromatic hydrocarbons and promoted the decomposition of light tar (with 1–2 aromatic rings). The results also indicated that the catalytic activity of potassium on tar decomposition exists in both solid and gas phases. Because alkali salts can be recovered from product gas as an aqueous solution, alkali-catalyzed gasification of woody biomass can be a promising process to produce clean product gas from the entrained-flow gasification process at a relatively low temperature.
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