| 1. |
- Ghorbani, Ramin, 1981-
(författare)
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Real-time breath gas analysis of carbon monoxide : laser-based detection and pulmonary gas exchange modeling
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Breath gas analysis is a promising approach for non-invasive medical diagnostics and physiological monitoring. Real-time, breath-cycle resolved biomarker detection facilitates data interpretation and has the potential to improve the diagnostic value of breath tests as exhalation profiles carry spatiotemporal information about biomarker origin and gas exchange in the respiratory tract. This thesis presents and scrutinizes a novel methodology for the analysis of real-time breath data, where single-exhalation profiles are simulated using a pulmonary gas exchange model and least-squares fitted to measured expirograms to extract airway and alveolar contributions and diffusing capacities. The methodology is demonstrated on exhaled breath carbon monoxide (eCO), a candidate biomarker for oxidative stress and respiratory diseases. The thesis mainly covers (1) the construction of a compact optical sensor based on tunable diode laser absorption spectroscopy (TDLAS) in the mid-infrared region (4.7 μm) for selective and precise real-time detection of CO in breath and ambient air (detection limit 9 ± 5 ppb at 0.1 s), (2) the design of an advanced online breath sampling system, (3) the implementation of a trumpet model with axial diffusion (TMAD) to simulate the CO gas exchange, and (4) the application of extended eCO analysis in clinical studies to establish the healthy non-smoker baseline of the eCO parameters and to study the response to CO and wood smoke exposure. It is shown that the TMAD adequately describes the gas exchange during systemic CO elimination for different breathing patterns, and that there is no difference between eCO parameters from mouth- and nose exhalations. Expirogram shape and eCO parameters exhibit a dependence on the exhalation flow rate, but for a given breathing maneuverer, the parameters lie in a narrow range. Airway CO is close to and correlates with ambient air CO, indicating negligible airway production in the healthy population. The alveolar diffusing capacity is independent of endogenous CO, even after exposure to elevated exogenous CO, and could be used to assess lung diffusion abnormalities. Compared to CO exposure, no clear additional effect of exposure to wood smoke particles on eCO is observed. The discrimination between endogenous and exogenous CO sources remains a challenge.
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| 2. |
- Hedayati, Ali, 1984-
(författare)
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Ash transformation in thermochemical conversion of different biomass resources with special focus on phosphorus
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- A great potential exists for increasing the use of bioenergy in thermochemical processes by utilizing agricultural biomass, forest residues, and sewage sludge that have high availability. Many of these biomass assortments have high ash contents with relatively high concentrations of ash-forming elements such as potassium (K), calcium (Ca), silicon (Si), and phosphorus (P). These elements can, during thermal conversion, cause several ash-related problems, such as deposit formation, slagging, and particle emissions. In particular, P has been found to play a vital role in such ash-related problems even at relatively low concentrations. In addition, ashes obtained from these biomass assortments could be an important source of valuable elements such as P and K. Therefore, detailed knowledge about the ash transformation and fate of P during thermal conversion of these opportunity biomass resources is of immense importance to mitigate ash-related problems and to recover valuable nutrient elements from the ash. The overall objective of this work was to determine the ash transformation and fate of P during single-pellet and fixed-bed combustion/gasification of different opportunity biomass fuels in the process temperature range of 600-1250°C. Different agricultural biomasses (poplar, wheat straw, grass, and wheat grain residues), forest residues (bark and twigs), and sewage sludge (pure and in mixtures with agricultural residues) were used. These fuels cover a wide range of overall ash compositions and different chemical associations of P in the fuel. The bark and poplar represent fuels rich in K and Ca with minor P content. The wheat straw, grass, and twigs represent typical Si- and K-rich fuels with minor to moderate P contents. The wheat grain residues (WGR) represent typical K- and P-rich fuels with a significant amount of Mg. The produced residual materials, i.e., char, different ash fractions and fine flue gas particles, were morphologically and chemically characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, inductively coupled plasma, and ion chromatography. The interpretation of the results was supported by thermodynamic equilibrium calculations. For all fuels, a major part of the P (> 80%) was found in coarse ash fractions because the studied process conditions favored the formation of stable condensed phosphates. The thermal conversion atmosphere (i.e., gasification/combustion) only caused small effects on the P release and the speciation of the P-compounds formed. Ash transformation pathways generally lead to the formation of orthophosphates (PO43-) such as Ca5(PO₄)3(OH), CaKPO4, and Ca3(PO4)2 with the partial substitution of Ca by some cation forming elements (Fe, Mg, and/or K), as the main P containing crystalline phases. Crystalline pyrophosphate (P2O74-) compounds were also found in the residual ashes from the seed-based fuel (WGR), where P originates from phytate in the biomass. For the fuels containing a certain (sufficient) amount of Si, orthophosphates interact with silicate phases to form both amorphous and crystalline phosphosilicates. For the sewage sludge mixtures, a surplus of available K was needed to form K-bearing phosphates due to side reactions of K with Si and Al. The chemical form of P in the formed ash residues is thus strongly dependent on both the type of P association in the fuel and the relative concentrations of other major ash-forming elements, such as K, Ca, Si, and Al. For the fuels with a high (Ca+Mg)/P molar ratio (AER), i.e., for the typical wood-derived fuels bark and poplar, hydroxyapatite was the main P-containing crystalline phase found in the ash. For the studied fuels/fuel mixtures with moderate AER and a high (K+Na)/(Si+Al) molar ratio (AR), e.g., twigs, grass, wheat straw, and sewage sludge with high mixtures of agricultural residues, there was also a possibility to form alkali-bearing phosphates such CaKPO4 and K-Mg whitlockite, besides hydroxyapatite. Since these fuels contain a high amount of Si, the P can be found in both amorphous phases, i.e. phosphosilicate, and Si substituted crystalline phases, i.e. Ca10(SiO4)x(PO4)6-XOH2-x and Ca15(PO4)2(SiO4)6. For fuels with moderate AER and low AR, e.g., pure sewage sludge and sewage sludge with low mixtures of agricultural residues, K-bearing phosphates were not formed. Instead, P was found in phases such as whitlockite and phosphosilicates. For the WGR fuel with relatively low AER and high AR, K-bearing phosphates were formed in the ashes, where the P was found in crystalline K-Mg/Ca pyrophosphates and K-Mg orthophosphate, as well as amorphous K-Mg-Ca phosphates. The produced knowledge can potentially be used to, e.g., i) suggest efficient measures to mitigate ash-related problems associated with P during thermochemical conversion of opportunity biomass fuels, ii) suggest potential pathways to form plant-available phosphates directly in the thermal conversion process to enable recovery of P and K from the obtained ashes, and iii) find optimal thermal conversion process conditions to obtain bio charcoals that are suitable as alternative fuels and reducing agents in the metallurgical industry.
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| 3. |
- Fagerström, Jonathan, 1984-
(författare)
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Fine particle emissions and slag formation in fixed-bed biomass combustion : aspects of fuel engineering
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- There is a consensus worldwide that the share of renewable energy sources should be increased to mitigate climate change. The strive to increase the renewable energy fraction can partly be met by an increased utilization of different biomass feedstocks. Many of the "new" feedstocks puts stress on certain challenges such as air pollution emissions and operation stability of the combustion process. The overall objective was to investigate, evaluate, and explain the effects of fuel design and combustion control - fuel engineering - as primary measures for control of slag formation, deposit formation, and fine particle emissions during biomass combustion in small and medium scale fixed-bed appliances. The work in this thesis can be outlined as having two main focus areas, one more applied regarding fuel engineering measures and one more fundamental regarding the time-resolved release of ash forming elements, with particular focus on potassium.The overall conclusion related to the abatement of particle emissions and slag formation, is that the release of fine particle and deposit forming matter can be controlled simultaneously as the slag formation during fixed-bed biomass combustion. The methodology is in this perspective denoted “fuel engineering” and is based on a combined approach including both fuel design and process control measures. The studies on time-resolved potassium release showed that a Macro-TG reactor with single pellet experiments was a valuable tool for studying ash transformation along the fuel conversion. The combination of dedicated release determinations based on accurate mass balance considerations and ICP analysis, with phase composition characterization by XRD, is important for the understanding of potassium release in general and time-resolved data in particular. For wood, the results presented in this work supports the potassium release mechanism from "char-K" but questions the previously suggested release mechanism from decomposition of K-carbonates. For straw, the present data support the idea that the major part of the potassium release is attributed to volatilization of KCl. To further explore the detailed mechanisms, the novel approach developed and applied in this work should be complemented with other experimental and analytical techniques.The research in this thesis has explored some of the challenges related to the combined phenomena of fuel conversion and ash transformation during thermochemical conversion of biomass, and has contributed with novel methods and approaches that have gained new knowledge to be used for the development of more effective bioenergy systems.
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