The improvement of the indicated thermal efficiency of an argon power cycle (replacing nitrogen with argon in the combustion reaction) is investigated in a CFR engine at high compression ratios in homogeneous charge compression ignition (HCCI) mode. The study combines the two effects that can increase the thermodynamic efficiency as predicted by the ideal Otto cycle: high specific heat ratio (provided by argon), and high compression ratios. However, since argon has relatively low heat capacity (at constant volume), it results in high in-cylinder temperatures, which in turn, leads to the occurrence of knock. Knock limits the feasible range of compression ratios and further increasing the compression ratio can cause serious damage to the engine due to the high pressure rise rate caused by advancing the combustion phasing. The technique proposed in this study in order to avoid intense knock of an argon cycle at high compression ratios is to cool the intake charge to subzero temperatures which leads to lower in-cylinder temperatures and hence, less possibility of having knock. The main variable in this study was the intake temperature which was investigated at 40.0 °C and -6.0 °C which corresponded to low and high compression ratios, respectively. Emission analysis shows that the low in-cylinder temperature of the cooled case led to less complete combustion, and so, lower combustion efficiency. Since nitrogen is replaced with argon, NOx was only formed in negligible amounts due to some nitrogen traces in the used gasses cylinders. Furthermore, the cooled charge required more work to be done in the gas exchange process due to the decrease in the intake pressure caused by cooling the intake which deteriorated the gas exchange efficiency. The heat losses factor was found to be the main parameter that dictated the improvement of the thermodynamic efficiency and it was found that the indicated thermal efficiency was deteriorated for the cooled case as a result of all the aforementioned factors. Although the values of the thermodynamic efficiency at high compression ratios did not meet the expectations based on the ideal Otto cycle due to the assumptions of the ideal cycle, the obtained values, in general, are relatively high.

Carbon Capture and Storage (CCS) is a legitimate technology option that should be part of a balanced portfolio of mitigation technologies available Post-Kyoto Protocol framework after Paris 2015 and beyond the 2020s or the cost achieving 2 degrees Celsius stabilisation scenario will significantly increase. Oxy-fuel combustion as a CCS technology option increases fuel flexibility. Additionally, oxy-biomass as a bio-energy with CCS (BECCS) technology can achieve negative carbon dioxide (CO2) emissions in sustainable biomass systems. Also, oxygen (O2) production in an air separation unit (ASU) gives potential for extra operational flexibility and energy storage. In this work, new designs of 20 litre spherical (R-20) and 30 litre non-spherical (R-30) ignition chambers have been built at the University of Edinburgh to carry-out dust ignition experiments with different ignition energies for evaluating pulverised fuel ignitability as a function of primary recycle (PR) O2 content for oxy-fuel PF milling safety. A set of coals and biomasses being used (at the time of submitting this work) in the utility pulverised fuel boilers in the UK have been employed. Coal and biomass dusts were ignited in air and oxy-fuel mixtures up to 30 % v/v O2 balance mixture CO2 where peak pressures (Pmax) from ignition were recorded. Pressure ratios (Pmax/Pinitial) were determined the key parameter for positive ignition identification with a value above 2.5 to be considered positive. Particle size effects in coal and biomass ignition were evaluated. Results on biomass were more variable than with coals, requiring a stronger ignition source (5,000 J) mainly due to larger particle sizes. Finer biomass particles behaved similarly to air ignition in 25 % v/v O2 in CO2. Larger particles of biomass did not ignite at all for most cases even reaching 30 % v/v O2 in CO2. A reference coal used, El Cerrejon, behaved as expected with 30 % v/v O2 balance CO2 matching air case; particles between 75-53 microns had lower ignitability than finer below 53 microns but were critical in devolatilisation. Most fuels did not ignite in 21 % v/v in CO2 below 200 g/m3 concentrations. The use of adequate ignition energy strength is needed for the PF mill safety case, with 5,000 J energy required for the biomasses tested. An indication of potential ignition chamber volume and geometry effect has also been observed when comparing results from R-20 and R-30 ignition chambers. Important implications include that oxy-biomass PR with 21 % v/v O2 content would give improved pulverised fuel (PF) milling safety when compared to air firing but reduced ignitability and a 25 % v/v O2 balance CO2 atmosphere would approach to oxy-biomass ignition behaviour in air in mills.

Production in Canada’s oil sands has been increasing, with a projected rate of 4.5 million barrels per day by 2025. Two production techniques are currently used, mining and in-situ, with the latter projected to constitute ~57% of all production by that time. Although in-situ extraction methods such as Steam Assisted Gravity Drainage (SAGD) are less invasive than mining, they result in more greenhouse gas (GHG) emissions per barrel and require large amounts of water that must be treated and recycled with a make-up water requirement of about 10%. CanmetENERGY is developing a steam generation technology called the High Pressure Oxy-fired Direct Contact Steam Generator (HiPrOx/DCSG, or DCSG for short) that will reduce these water requirements and sequester GHGs. This study evaluates the technical feasibility of this technology using process simulations, bench-scale testing, and pilot-scale testing. At first, a method in which to integrate the DCSG into the SAGD process was presented and process modeling of expected system performance was undertaken. The process simulations indicated that DCSG decreased the energy intensity of SAGD by up to 7.6% compared to the base SAGD case without carbon capture and storage (CCS), and up to 12.0% compared to the base SAGD case with CCS. Bench-scale testing was then performed using a pressurized thermogravimetric analyzer (PTGA) in order to investigate the effects of increased pressure and high moisture environments on a Canadian lignite coal char’s reactivity. It was found that under reaction kinetic-controlled conditions at atmospheric pressure, the increased addition of steam led to a reduction in burning time. The findings may have resulted from the lower heat capacity and higher thermal conductivity of steam compared to CO2. At increased pressures, CO2 inhibited burnout due to its higher heat capacity, lower thermal conductivity, and its effect on C(O) concentrations on the particle surface. When steam was added, the inhibiting effects of CO2 were counteracted, resulting in burnout rates similar to pressurized O2/N2 environments. These preliminary results suggested that the technology was feasible at a bench-scale level. Conflicting literature between bench-scale and pilot-scale studies indicated that pilot-scale testing would be advantageous as a next step. At the pilot-scale, testing was performed using n-butanol, graphite slurry, and n-butanol/graphite slurry mixtures covering lower and upper ends in fuel reactivity. It was found that stable combustion was attainable, with high conversion efficiencies in all cases. With the n-butanol, it was possible to achieve low excess oxygen requirements, which minimizes corrosion issues and reduce energy requirements associated with oxygen generation. With graphite slurry, it was found that it was possible to sustain combustion in these high moisture environments and that high conversion was achieved as indicated by the undetectable levels of carbonaceous materials observed in downstream equipment. Overall, these studies indicate that DCSG is technically feasible from the perspectives of energy and combustion efficiencies as well as from a steam generation point of view. Future work includes the investigation of possible corrosion associated with the product gas, the effect of CO2 on bitumen production, the nature of the mineral melt formed by the deposition of the dissolved and suspended solids from the water in the combustor, and possible scaling issues in the steam generator and piping associated with mineral deposits from the dissolved and suspended solids in the produced water is recommended.

Production in Canada’s oil sands has been increasing, with a projected rate of 4.5 million barrels per day by 2025. Two production techniques are currently used, mining and in-situ, with the latter projected to constitute ~57% of all production by that time. Although in-situ extraction methods such as Steam Assisted Gravity Drainage (SAGD) are less invasive than mining, they result in more greenhouse gas (GHG) emissions per barrel and require large amounts of water that must be treated and recycled with a make-up water requirement of about 10%. CanmetENERGY is developing a steam generation technology called the High Pressure Oxy-fired Direct Contact Steam Generator (HiPrOx/DCSG, or DCSG for short) that will reduce these water requirements and sequester GHGs. This study evaluates the technical feasibility of this technology using process simulations, bench-scale testing, and pilot-scale testing. At first, a method in which to integrate the DCSG into the SAGD process was presented and process modeling of expected system performance was undertaken. The process simulations indicated that DCSG decreased the energy intensity of SAGD by up to 7.6% compared to the base SAGD case without carbon capture and storage (CCS), and up to 12.0% compared to the base SAGD case with CCS. Bench-scale testing was then performed using a pressurized thermogravimetric analyzer (PTGA) in order to investigate the effects of increased pressure and high moisture environments on a Canadian lignite coal char’s reactivity. It was found that under reaction kinetic-controlled conditions at atmospheric pressure, the increased addition of steam led to a reduction in burning time. The findings may have resulted from the lower heat capacity and higher thermal conductivity of steam compared to CO2. At increased pressures, CO2 inhibited burnout due to its higher heat capacity, lower thermal conductivity, and its effect on C(O) concentrations on the particle surface. When steam was added, the inhibiting effects of CO2 were counteracted, resulting in burnout rates similar to pressurized O2/N2 environments. These preliminary results suggested that the technology was feasible at a bench-scale level. Conflicting literature between bench-scale and pilot-scale studies indicated that pilot-scale testing would be advantageous as a next step. At the pilot-scale, testing was performed using n-butanol, graphite slurry, and n-butanol/graphite slurry mixtures covering lower and upper ends in fuel reactivity. It was found that stable combustion was attainable, with high conversion efficiencies in all cases. With the n-butanol, it was possible to achieve low excess oxygen requirements, which minimizes corrosion issues and reduce energy requirements associated with oxygen generation. With graphite slurry, it was found that it was possible to sustain combustion in these high moisture environments and that high conversion was achieved as indicated by the undetectable levels of carbonaceous materials observed in downstream equipment. Overall, these studies indicate that DCSG is technically feasible from the perspectives of energy and combustion efficiencies as well as from a steam generation point of view. Future work includes the investigation of possible corrosion associated with the product gas, the effect of CO2 on bitumen production, the nature of the mineral melt formed by the deposition of the dissolved and suspended solids from the water in the combustor, and possible scaling issues in the steam generator and piping associated with mineral deposits from the dissolved and suspended solids in the produced water is recommended.

Oxy-fuel combustion is an enabling technology for capture of CO2 from coal combustion, the economics of which depends strongly on the ability of the process to produce low NOX emissions. The literature contains many reports of lower NOX emissions from oxy-fuel combustion but the reasons for this are not fully understood. The objective of this work was to gain understanding of nitrogen evolution under pulverized coal oxy-fuel conditions. Pulverized coal was burned in a once-through, down-fired, laminar flow reactor. Nitrogen compounds and other combustion species were measured at the reactor centerline as a function of distance from the burner. Dry recycled flue gas was simulated with CO2 and O2 was added to form an oxy-fuel oxidizer. Oxy-fuel combustion measurements were compared to similar experimental data from air-fired cases. In addition, a detailed kinetic model was written and nodel predictions were compared to the experimental data. These comparisons gave insight into the mechanisms of nitrogen evolution under oxy-fuel conditions. The combustion model matched the experimental data well in many qualitative respects but failed to predict reburning reactions which are believed to be important in both air and oxy-fuel combustion. Model assumptions related to particle size and mixing may be responsible for this difference. Several mechanisms other than reburning are discussed with respect to their importance in the results. The effect of varying primary combustion zone stoichiometry (depth of staging) was investigated and it was found that oxy-fuel combustion, like air combustion has some depth of staging that produces minimum NOX. At minimum NOX conditions in this once-through experiment both air and oxy-fuel combustion converted a similar amount of fuel-bound nitrogen to NOX, however the minimums were at significantly different stoichiometries. Relative to air combustion, oxy-fuel combustion was found to exhibit higher concentrations of CO, NH3, HCN, and hydrocarbons, which indicates a more effective reburning environment exists in oxy-fuel combustion relative to air, even at higher primary stoichiometric ratios. This and other factors such as maximizing the amount of recycled NOX passing through the fuel-rich flame lead to the conclusion that oxy-fuel combustors should be operated at higher primary stoichiometric ratios than air combustors, which would conveniently also favor high fuel burnout.

Le dioxyde de carbone, provenant de la combustion d’énergies fossiles, est l’un plus important gaz à effet de serre. La réduction des émissions de CO2 à l’atmosphère s’imposant, une solution consiste en la capture et la séquestration du CO2 par oxy-combustion. Avant l’étape de séquestration, le CO2 doit être purifié. Les procédés de séparation des gaz nécessitent une bonne connaissance des propriétés thermodynamiques des équilibres entre phases. C’est pourquoi un nouvel appareil expérimental, permettant l’étude de la solubilité d’un mélange de gaz (CO2, O2, NOx, SO2) dans des solutions aqueuses, a été développé. Dans un premier temps, l’étude du système CO2-eau a permis de valider l’appareil expérimental pour les domaines de température et de pression de l’étude (293 ,15-393,15 K, jusqu’à 5 MPa). Ensuite, les données sur le système CO2-eau-NaOH étant rares dans la littérature, ce système a été étudié. Les données expérimentales obtenues ont été comparées à un modèle développé dans l’étude. Les modèles de coefficient d’activité de Pitzer et de NRTL électrolyte sont comparés. La dernière étape de l’étude est l’optimisation des paramètres du modèle NRTL-e par ajustement sur les données expérimentales. / Production of carbon dioxide from burning fossil fuel participates in the global warming. This issue generates a growing interest for CO2 capture and storage from oxy fuel combustion. Before the sequestration step, the CO2 has to be purified from impurities. Separation processes require a good knowledge of thermodynamics properties of phase equilibria. In this context a new experimental device was designed and set up in the LaTEP to allow the study of the solubility of gas mixture involved in CO2 capture and storage processes (CO2, O2, NOx, SO2). The apparatus was, first, validated by studying the CO2-water system in the temperature range from 293.15 K to 393.15 K and at pressure up to 5 MPa. Then, the CO2-water-NaOH was studied because few data are available in the scientific literature. Experimental data obtained was compared with a model developed in this work. This model is based on a thermodynamic description of physical chemical phenomena occuring in a vapour liquid system. Two model of activity coefficient are compared (Pitzer and electrolyte-NRTL). The last step of this study is the parameter optimization for e-NRTL.

In this study the catalytic pyrolysis and combustion characteristics of Turkish coal samples in O2/N2 and O2/CO2 (oxy-fuel conditions) ambient conditions were explored and the evolution of emissions during these tests was investigated using non-isothermal Thermo-gravimetric Analysis (TGA) technique combined with Fourier Transform Infrared (FTIR) spectroscopy. Potassium carbonate (K2CO3), calcium hydroxide (Ca(OH)2), iron (III) oxide (Fe2O3) and iron (III) chloride (FeCl3) were employed as precursors of catalysts to investigate the effects of potassium (K), calcium (Ca) and iron (Fe). Furthermore the effects of these catalysts on calorimetric tests of Turkish coal samples were investigated. TGA-FTIR pyrolysis tests were carried out in 100 % N2 and 100 % CO2 ambient conditions which are the main diluting gases in air and oxy-fuel conditions. Lignite pyrolysis tests revealed that the major difference between pyrolysis in these two ambient conditions was observed beyond 720

Die Herleitung des Unterschieds zwischen globaler und lokaler Stöchiometriezahl für den Oxyfuel-Prozess hat gezeigt, dass gleiche lokale Stöchiometriezahlen bei variierendem Rezirkulationsanteil unterschiedliche globale Stöchiometriezahlen zur Folge haben. In dieser Arbeit wird vorgeschlagen, die Bezeichnung der Zustandspunkte im Oxyfuel-Prozess mit den Sauerstoffkonzentrationen am Brennkammereintritt bzw. -austritt zu verbinden. Für den Sauerstoffanteil am Brennkammereintritt (z.B. 30 vol.-%) und den Restsauerstoff am Brennkammerende (z.B. 4 vol.-%) folgt zum Bespiel die Bezeichnung Oxyfuel 30 mit 4 % Restsauerstoff. Diese Bezeichnung ist eindeutig und kann das Lambda – als Beschreibung der Stöchiometrie im konventionellen Betrieb – ablösen. Für eine Vielzahl an Punkten sind Verbrennungsversuche mit Trockenbraunkohle und Sauerstoff durchgeführt worden. Ein stabiler Betrieb der Versuchsanlage der TU Dresden wurde zwischen Oxyfuel 17 und Oxyfuel 33 erreicht. Die Untersuchungen haben nachgewiesen, dass die Rezirkulation des feuchten Abgases für die Verbrennung unkritisch ist. Die Schwefeldioxid-Emissionen sind abhängig von den variierenden Reaktionstemperaturen im Kennfeld, dem Restsauerstoff am Brennkammerende und der Rezirkulation des Abgases. Mit der Belagssondenmessung von Aschepartikeln im Abgasstrom wurde gezeigt, dass auch andere Komponenten (z.B. Chlor) im Oxyfuel-Prozess aufkonzentriert werden. Diese erhöhten Konzentrationen werden zu neuen Anforderungen in der Werkstoffauswahl führen. Für das Einschwingverhalten der Abgaszusammensetzung beim Umschalten von konventioneller Verbrennung zu Oxyfuel-Prozess-Fahrweise hat sich gezeigt, dass für diese Staubfeuerungs-Versuchsanlage ein einfaches Rührkesselmodell geeignet ist.

Pollution is one of the greatest concerns with pulverized coal combustion. With tightening standards on pollution emissions, more information is needed to create better design models. Burner modifications are the most efficient changes that can be made to assure sufficient carbon burnout and low NOx emissions. Experiments were performed in the BYU Flat Flame Burner (FFB) lab, operating under fuel rich conditions for pyrolysis experiments and fuel lean conditions for char oxidation experiments. Effects of temperature, coal rank, residence time, and post flame oxygen content on mass release, nitrogen release, and reactivity were examined. Elemental and Inductively coupled plasma (ICP) analyses were used to determine the mass and nitrogen release of coals and chars. FT-IR was used to determine gas phase nitrogen compositions on selected experiments. Results of char oxidation experiments were fit to a first-order model to obtain an Arrhenius pre-exponential factor, while activation energies were approximated using a published correlation. CPD model calculations were used to find experimental residence times and particle diameters that obtained full pyrolysis yields. Oxy-fuel experiments were performed by switching the burner diluent gas from N2 to CO2. Oxy-fuel experiments exhibited a rank effect in nitrogen release. Bituminous coal tests showed no statistically significant difference in mass or nitrogen release between the two conditions. A sub-bituminous coal exhibited a greater mass and nitrogen release for the same residence time under the CO2 environment, which could be due to early gasification of the char. Two samples of a chemically treated coal with different additive concentrations were tested against an untreated sample for combustion enhancement. The treated samples showed an increase on the order of 15% absolute in pyrolysis yield compared to the untreated sample. An increase in reactivity on the order of 35% was observed for the higher concentrated sample, but not for the lower treatment concentration. Gas phase nitrogen measurements showed both HCN and NH3 at the 1300 K gas temperature condition. HCN and NH3 release during pyrolysis was largely rank dependent, with more HCN formed initially than NH3 for 5 of the 6 samples. However, a Polish bituminous coal was found to have more NH3 than HCN. These nitrogen species data can be used to evaluate or refine nitrogen transformation mechanisms.

A new method of power production, called pressurized oxy-fuel combustion, burns coal with CO2 and oxygen, rather than air, bringing us closer to the end goal of developing zero emission coal-fired utility boilers. However, high-pressure, high-temperature systems such as these are under-studied, and their behavior is difficult to measure. An accurate model for previously untested conditions requires data for validation. The heat release profile of flames and their radiative intensity is one of the key data sets required for model validation of an oxy-coal combustion system. A radiometer can be used to obtain the necessary radiative heat flux data. However, several studies show significant measurement errors of past radiometer designs. This work focuses on developing a narrow angle radiometer that can be used to describe radiative heat transfer from a pressurized oxy-coal flame. The sensitivity of the instrument to outside environmental influences is thoroughly examined, making it possible to obtain the axial radiative heat flux profile of the flame in a 100kW pressurized facility by accurately converting the measured quantities into radiative heat flux. Design aspects of the radiometer are chosen to improve the accuracy of radiative heat flux measurements as well as conform to the physical constraints of the 100kW pressurized facility. The radiometer is built with a 0.079-inch aperture, an 8.63-inch probe internally coated with high emissivity coating, four baffles spaced evenly down the length of the probe, no optic lens, a thermopile as the sensor, argon purge gas, and a water-cooled jacket. The radiometer has a viewing angle of 1.33 degrees. The instrument is calibrated with a black body radiator, and these calibration data are used in combination with radiation models to convert the radiometer signal in mV to radiative heat flux in kW/m2. Environmental factors affecting accuracy are studied. The results of the calibration data show that the radiometer measurements will produce a calculated heat flux that is accurate to within 5.98E-04 kW/m2.