Master of Science / Geology / Matthew W. Totten / The thermal maturity of hydrocarbon-rich source rocks can be estimated by several different methods. These methods focus on a specific geochemical or mineralogical aspect contained within the rock. Because each method has limitations, it is advisable to use several methods to better determine thermal maturation. This report summarizes two common methods used to determine thermal maturity, vitrinite reflectance and illitization. Vitrinite reflectance and illitization have both been shown to be effected by similar temperatures that are within the hydrocarbon generation window. In some previous studies these two methods give different levels of maturation when looked at in tandem. Formations such as the Woodford Shale of Oklahoma are made up almost completely of illite in the clay fraction, even at low levels of vitrinite reflectance. These are also without a clear source of potassium, which is often the limiting factor in the process of illitization. Totten et al. (2013) suggest that in place of potassium feldspars, which are a common source of K⁺ for illite (but lacking in the Woodford) that the needed K⁺ was provided by the organic material that was being altered under the same temperatures of the clay minerals. The Woodford contains large amounts of organic matter, This would be consistent with promoting illitization at lower thermal maturities than organic-poor shales.

Anomalously high groundwater salinities exist within the syn-impact sediment of the Chesapeake Bay impact crater, including an unexplained brine. This brine may be the result of phase-separation of seawater that occurred within the syn-impact sediments as underlying deformed and possibly melted basement rock cooled following impact. The 85 km wide crater has been described as a complex peak-ring crater; created 35.8 million years ago in the then submerged unconsolidated sediments of the Atlantic Coastal Plain and now completely buried by post-impact sediments. An annular trough with relatively undisturbed basement surrounds a ~38 km diameter inner basin with a peak ring and central uplift. The basement surface within the inner basin was modified by the impact and is projected to be approximately 1.6 km below sea level. Geothermometry and advective and conductive heat flow modeling was performed to characterize a possible post-impact hydrothermal system. Thermal maturity and radiogenic techniques were used to estimate the temperature history of the crater sediments. Core samples from one borehole just outside the crater, two within the annular trough, and one shallow borehole within the inner basin were examined. Numerical heat and fluid flow models were developed using a range of likely sediment parameters and basal heat flow values to determine if phase-separation temperatures were likely to have occurred, and to evaluate what affect, if any, lithostatic overpressures may have had on post-impact cooling. Geothermometry results indicate that no detectable thermal anomaly exists within the syn or post-impact sediments at these boreholes; however, no data are available within the deep inner basin where temperatures were likely to have been higher. Samples from existing boreholes suggest that sediment are organically immature and likely were never heated above ~40°C for a geologically significant period of time. These results support apatite He (U/Th) and previously published apatite fission track radiogenic ages indicating no Cenozoic resetting. Heat flow simulations indicate that a high temperature (>400°C) hydrothermal system could have existed within the inner basin and not caused any measurable effect on thermal maturity in the annular trough and shallow portion of the inner basin. Results also indicate that phase-separation could have occurred in the syn-impact sediments using reasonable estimates of basal heat flow, permeability, thermal conductivity, and porosity values, and that overpressures resulting from rapid deposition of syn-impact sediments dissipate within a few thousand years and are not an important heat transport mechanism. / Master of Science

Σκοπός της εργασίας είναι η μελέτη της ωριμότητας της οργανικής ύλης ορισμένων σχηματισμών της Ιόνιας Ζώνης, όπως οι αργιλικοί σχίστες του ανώτερου και κατώτερου Ιουρασικού, ο Ανώτερος Πυριτικός Ορίζοντας της Βίγλας του Κρητιδικού και οι βιτουμενιούχοι Ψαμμίτες του Τριτογενούς, χρησιμοποιώντας τεχνικές Οργανικής Πετρολογίας. Τα δείγματα συλλέχθηκαν από επιφανειακές εμφανίσεις στην Ήπειρο. Αρχικά χρησιμοποιήθηκαν οξέα (HCl-HF) για να απομακρυνθεί το μεγαλύτερο μέρος των ανθρακικών και πυριτικών ορυκτών. Το συμπύκνωμα που προέκυψε, αναμίχθηκε με ZnCl2 συγκεκριμένης πυκνότητας, ώστε να επέλθει βαρυτικός διαχωρισμός του πετρώματος σε ελαφρύ και βαρύ κλάσμα. Το οργανικό μέρος οξειδώθηκε χημικά για να υπολογιστεί η περιεκτικότητα σε Ολικό Οργανικό Άνθρακα. Στιλπνές τομές παρασκευάστηκαν με ανάμιξη του οργανικού υλικού με διάλυμα εποξικής ρητίνης και μελετήθηκαν στο ανθρακοπετρογραφικό μικροσκόπιο. Έμφαση δόθηκε στην ανακλαστικότητα βιτρινίτη και τον προσδιορισμό των maceral. Εφαρμόστηκε επίσης περιθλασιμετρία ακτίνων Χ για να προσδιοριστεί η ορυκτολογική σύσταση των πετρωμάτων. Διαπιστώθηκε ότι οι αργιλικοί σχίστες του κατώτερου Ιουρασικού περιέχουν οργανική ύλη (TOC: 4,74%), ο βαθμός ωριμότητας (Rr 0,68%) της οποίας βρίσκεται εντός του παραθύρου πετρελαίου. Ωστόσο περαιτέρω έρευνα εστιασμένη στους Κατω-Ιουρασικούς αργιλικούς σχίστες με Posidonia, με τη βοήθεια της Οργανικής Πετρολογίας και της πυρόλυσης Rock-Eval είναι αναγκαία, προκειμένου να διαπιστωθεί η ποιότητά τους ως μητρικά πετρώματα υδρογονανθράκων. / The main objective of this paper is to study by means of Organic Petrology techniques, the maturity of the dispersed organic matter from certain sedimentary formations of the Ionian Zone, such as the Bituminous Shale, the Upper Siliceous Vigla Formation and the Bituminous Sandstone. The samples were collected from outcropping sites located in the region of Epirus. Initially they were treated with acids (HCl-HF) to remove most of the carbonate and silicate minerals. Then a ZnCl2 solution was used to concentrate the organic-rich fraction. Total Organic Carbon (TOC) content was determined applying dichromate oxidation. Polished blocks were prepared from the concentrated organic matter mounted in epoxy resin and examined under the coal-petrography microscope. Emphasis was given to maceral identification and vitrinite reflectance (Rr) measurements, which provide information regarding the quality and the maturity of the organic matter respectively, with implications for the petroleum generation potential regardless the level of alteration. The TOC and Rr values (4.74% and 0.68%, respectively) confirm to the oil potential of the Lower Jurassic Posidonia Shale. Nevertheless, it is suggested that detailed and higher resolution sampling focusing on the Lower Posidonia Shale, as well as organic petrography analyses coupled with Rock-Eval pyrolysis should be carried out in order to accurately determine its quality as petroleum source rocks.

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22424号 / 工博第4685号 / 新制||工||1731(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 林 為人, 教授 小池 克明, 准教授 村田 澄彦 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

With increasing energy demand globally and, in particular, in South Africa coupled with depletion of the earth’s fossil energy resources and growing problem of disposal of nonbiodegradable waste such as waste tyres, there is a need and effort globally to find alternative energy from waste material including waste tyres. One possible way of exploiting waste tyre for energy or chemicals recovery is through gasification for the production of syngas, and this is what was investigated in this study. The possibility of gasification of waste tyre blended with coal after pyrolysis was investigated and two Bituminous coals were selected for blending with the waste tyre in co-gasification. A sample of ground waste tyre / waste tire, WT, a high vitrinite coal from the Waterberg coalfield (GG coal) and a high inertinite coal from the Highveld coalfield (SF coal) were used in this investigation. The waste tyre sample had the highest volatile matter content of 63.8%, followed by GG coal with 27% and SF coal with 23.8%. SF coal had the highest ash content of 21.6%, GG coal had 12.6% and waste tyre had the lowest of 6.6%. For the chars, SF char still had the highest ash of 24.8%, but WT char had higher ash, 14.7%, when compared to GG char with 13.9% ash. The vitrinite content in GG coal was 86.3%, whilst in SF coal it was 25% and SF coal had a higher inertinite content of 71% when compared to GG coal with 7.7%. SF char had the highest BET surface area of 126m2/g, followed by GG char with 113m2/g, and WT had the lowest value of 35.09m2/g. The alkali indices of the SF, WT and GG chars were calculated to be 8.2, 4.2 and 1.7 respectively. Coal samples were prepared by crushing and milling to particle sizes less than 75μm before charring in a packed bed balance reactor at temperatures up to 1000oC.Waste tyre samples were charred at the same conditions before milling to < 75μm particle size. Coal and WT chars were blended in ratios of 75:25, 50:50 and 25:75 before gasification experimentation. Carbon dioxide gasification was conducted on the blends and the pure coal and WT chars in a Thermogravimetric analyser (TGA) at 900oC, 925oC, 950oC and 975oC and ambient pressure. 100% CO2 was used at a flow rate of 2L/min. Reactivity of the pure char samples was found to be in the order SF > GG > WT, and the relationship between the coal chars’ reactivities could be explained by the high ash content of the SF char and low reactivity of the WT char corresponds to its low BET surface area. In general, the coal/WT char mixtures were less reactive than the respective coal, but more reactive than the pure WT char, the only exception being the 75% GG char blend which was initially more reactive than the GG char, and reactivity decreased with increasing WT content. For all samples reactivity increased with increasing temperature. The relationship between the reactivities of the GG char and its blends and that of the SF char and its blends was found to be affected by the amount of WT char added, especially at the lower temperatures 900oC and 925oC. SF coal is more reactive than GG coal, but at 900oC and 925oC, the reactivity of GG/WT blends improves in relation to the SF/WT blends with an increase in the ratio of WT in the blends, i.e. the 25% GG char blend is more reactive than the 25% SF char blend. The reactivity of the coal/WT blends was also checked against predicted conversion rates based on the conversion rates of the pure WT and coal samples. At 900oC and 925oC, the reactivities of the blends of both coal chars with WT char were found to be greater than the predicted conversion rates, and for the GG/WT blends the deviation increased with increasing WT ratios, while for the SF/WT blends the deviation increased with increasing SF ratios. These findings suggest the presence of synergism or enhancement between the coal chars and WT char in gasification reactions. The random pore model (RPM) was used to model the gasification results and it was found to adequately describe the experimental data. Activation energies determined with the RPM were found to be 205.4kJ/mol, 189.9kJ/mol and 173.9kJ/mol for SF char, WT char and GG char respectively. The activation energies of the coal/WT blends were found to be lower than those of both the pure coal and the pure WT chars. For the GG/WT blends the activation energy decreased with increasing WT char ratio, while for the SF/WT blends the activation energy decreased with increasing SF char ratio. The trends of the activation energies and conversion rates of the blends point to synergism or enhancement between the coal and WT chars in CO2 gasification reactions, and in the GG/WT blends this enhancement is driven more by the WT char, while in SF/WT blends it is driven by SF chars. It is possible that enhancement of the reactions is caused by mineral matter catalysis of the gasification reactions. The ash contents and alkali indices of the pure samples follow the order SF > WT > GG. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

An investigation was undertaken to compare the kinetics of combustion and gasification reactions of chars prepared from two South African coals in different reaction atmospheres: air, steam, and carbon dioxide. The two original coals were characterised as vitrinite-rich (Greenside) and inertinite-rich (Inyanda) coals with relatively low ash content (12.5-16.7 wt. %, adb). Chars were prepared from the parent coals under nitrogen atmosphere at 900 °C. Characterisation results show that the volatiles and moisture were almost completely driven off from the parent coals, indicating that the pyrolysis process was efficient. Physicalstructural properties such as porosity and surface area generally increased from the parent coals to the subsequent chars. The heterogeneous char-gas reactions were conducted isothermally in a TGA on ~1 mm size particles. To ensure that the reactions are under chemical reaction kinetic control regime, different temperatures zones were selected for the three different reaction atmospheres. Combustion reactivity experiments were carried out with air in the temperature range of 387 °C to 425 °C; gasification reactivity with pure steam were conducted at higher temperatures (775 °C - 850 °C) and within 825 °C to 900 °C with carbon dioxide. Experimental results show differences in the specific reaction rate with carbon conversion in different reaction atmospheres and char types. Reaction rates in all three reaction atmospheres were strongly dependent on temperature, and follow the Arrhenius type kinetics. All the investigated reactions (combustion with air and gasification with CO2 and steam) were found to be under chemical reaction control regime (Regime I) for both chars. The inertinite-rich coals exhibit longer burn-out time than chars produced from vitrinite-rich coals, as higher specific reaction rate were observed for the vitrinite-rich coals in the three different reaction atmospheres. The determined random pore model (RPM) structural parameters did not show any significant difference during steam gasification of Greenside and Inyanda chars, whereas higher structural parameter values were observed for Greenside chars during air combustion and CO2 gasification (ψ > 2). However a negative ψ value was determined during CO2 gasification and air combustion of Inyanda chars. The RPM predictions was validated with the experimental data and exhibited adequate fitting to the specific rate of reaction versus carbon conversion plots of the char samples at the different reaction conditions chosen for this study. The activation energy determined was minimal for air and maximum for CO2 for both coals; and ranged from 127-175 kJ·mol-1 for combustion, 214-228 kJ·mol-1 and 210-240 kJ·mol-1 for steam and CO2 gasification respectively. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

With increasing energy demand globally and, in particular, in South Africa coupled with depletion of the earth’s fossil energy resources and growing problem of disposal of nonbiodegradable waste such as waste tyres, there is a need and effort globally to find alternative energy from waste material including waste tyres. One possible way of exploiting waste tyre for energy or chemicals recovery is through gasification for the production of syngas, and this is what was investigated in this study. The possibility of gasification of waste tyre blended with coal after pyrolysis was investigated and two Bituminous coals were selected for blending with the waste tyre in co-gasification. A sample of ground waste tyre / waste tire, WT, a high vitrinite coal from the Waterberg coalfield (GG coal) and a high inertinite coal from the Highveld coalfield (SF coal) were used in this investigation. The waste tyre sample had the highest volatile matter content of 63.8%, followed by GG coal with 27% and SF coal with 23.8%. SF coal had the highest ash content of 21.6%, GG coal had 12.6% and waste tyre had the lowest of 6.6%. For the chars, SF char still had the highest ash of 24.8%, but WT char had higher ash, 14.7%, when compared to GG char with 13.9% ash. The vitrinite content in GG coal was 86.3%, whilst in SF coal it was 25% and SF coal had a higher inertinite content of 71% when compared to GG coal with 7.7%. SF char had the highest BET surface area of 126m2/g, followed by GG char with 113m2/g, and WT had the lowest value of 35.09m2/g. The alkali indices of the SF, WT and GG chars were calculated to be 8.2, 4.2 and 1.7 respectively. Coal samples were prepared by crushing and milling to particle sizes less than 75μm before charring in a packed bed balance reactor at temperatures up to 1000oC.Waste tyre samples were charred at the same conditions before milling to < 75μm particle size. Coal and WT chars were blended in ratios of 75:25, 50:50 and 25:75 before gasification experimentation. Carbon dioxide gasification was conducted on the blends and the pure coal and WT chars in a Thermogravimetric analyser (TGA) at 900oC, 925oC, 950oC and 975oC and ambient pressure. 100% CO2 was used at a flow rate of 2L/min. Reactivity of the pure char samples was found to be in the order SF > GG > WT, and the relationship between the coal chars’ reactivities could be explained by the high ash content of the SF char and low reactivity of the WT char corresponds to its low BET surface area. In general, the coal/WT char mixtures were less reactive than the respective coal, but more reactive than the pure WT char, the only exception being the 75% GG char blend which was initially more reactive than the GG char, and reactivity decreased with increasing WT content. For all samples reactivity increased with increasing temperature. The relationship between the reactivities of the GG char and its blends and that of the SF char and its blends was found to be affected by the amount of WT char added, especially at the lower temperatures 900oC and 925oC. SF coal is more reactive than GG coal, but at 900oC and 925oC, the reactivity of GG/WT blends improves in relation to the SF/WT blends with an increase in the ratio of WT in the blends, i.e. the 25% GG char blend is more reactive than the 25% SF char blend. The reactivity of the coal/WT blends was also checked against predicted conversion rates based on the conversion rates of the pure WT and coal samples. At 900oC and 925oC, the reactivities of the blends of both coal chars with WT char were found to be greater than the predicted conversion rates, and for the GG/WT blends the deviation increased with increasing WT ratios, while for the SF/WT blends the deviation increased with increasing SF ratios. These findings suggest the presence of synergism or enhancement between the coal chars and WT char in gasification reactions. The random pore model (RPM) was used to model the gasification results and it was found to adequately describe the experimental data. Activation energies determined with the RPM were found to be 205.4kJ/mol, 189.9kJ/mol and 173.9kJ/mol for SF char, WT char and GG char respectively. The activation energies of the coal/WT blends were found to be lower than those of both the pure coal and the pure WT chars. For the GG/WT blends the activation energy decreased with increasing WT char ratio, while for the SF/WT blends the activation energy decreased with increasing SF char ratio. The trends of the activation energies and conversion rates of the blends point to synergism or enhancement between the coal and WT chars in CO2 gasification reactions, and in the GG/WT blends this enhancement is driven more by the WT char, while in SF/WT blends it is driven by SF chars. It is possible that enhancement of the reactions is caused by mineral matter catalysis of the gasification reactions. The ash contents and alkali indices of the pure samples follow the order SF > WT > GG. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

An investigation was undertaken to compare the kinetics of combustion and gasification reactions of chars prepared from two South African coals in different reaction atmospheres: air, steam, and carbon dioxide. The two original coals were characterised as vitrinite-rich (Greenside) and inertinite-rich (Inyanda) coals with relatively low ash content (12.5-16.7 wt. %, adb). Chars were prepared from the parent coals under nitrogen atmosphere at 900 °C. Characterisation results show that the volatiles and moisture were almost completely driven off from the parent coals, indicating that the pyrolysis process was efficient. Physicalstructural properties such as porosity and surface area generally increased from the parent coals to the subsequent chars. The heterogeneous char-gas reactions were conducted isothermally in a TGA on ~1 mm size particles. To ensure that the reactions are under chemical reaction kinetic control regime, different temperatures zones were selected for the three different reaction atmospheres. Combustion reactivity experiments were carried out with air in the temperature range of 387 °C to 425 °C; gasification reactivity with pure steam were conducted at higher temperatures (775 °C - 850 °C) and within 825 °C to 900 °C with carbon dioxide. Experimental results show differences in the specific reaction rate with carbon conversion in different reaction atmospheres and char types. Reaction rates in all three reaction atmospheres were strongly dependent on temperature, and follow the Arrhenius type kinetics. All the investigated reactions (combustion with air and gasification with CO2 and steam) were found to be under chemical reaction control regime (Regime I) for both chars. The inertinite-rich coals exhibit longer burn-out time than chars produced from vitrinite-rich coals, as higher specific reaction rate were observed for the vitrinite-rich coals in the three different reaction atmospheres. The determined random pore model (RPM) structural parameters did not show any significant difference during steam gasification of Greenside and Inyanda chars, whereas higher structural parameter values were observed for Greenside chars during air combustion and CO2 gasification (ψ > 2). However a negative ψ value was determined during CO2 gasification and air combustion of Inyanda chars. The RPM predictions was validated with the experimental data and exhibited adequate fitting to the specific rate of reaction versus carbon conversion plots of the char samples at the different reaction conditions chosen for this study. The activation energy determined was minimal for air and maximum for CO2 for both coals; and ranged from 127-175 kJ·mol-1 for combustion, 214-228 kJ·mol-1 and 210-240 kJ·mol-1 for steam and CO2 gasification respectively. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Tout mécanisme de formation d'un bassin sédimentaire porte une signature thermique caractéristique. Inversement, la reconstitution de l'histoire thermique d'un bassin sédimentaire permet d'en tirer des conclusions sur les mécanismes et l'histoire de sa formation. Les méthodes géothermométriques nous permettent d'étudier l'histoire thermique d'un bassin. Les enregistrements réalisés nous renseignent, soit sur les conditions de température (ou conditions T/P) instantanées (températures de fermeture, de cristallisation, etc.), soit sur les effets du couple température-temps (énergie) au cours de la diagenèse (transformation de la matière organique, transformation des minéraux argileux). Ce mémoire présente les résultats d'une étude réalisée dans l'avant-pays alpin de Suisse et de Haute-Savoie (France). Le bassin molassique s'étend le long du front externe de l'arc alpin sur plus de 800 km, de Chambéry à Vienne. Depuis le front alpin la sédimentation de la Molasse, essentiellement détritique, pro grade vers le nord-ouest. Cet élargissement du bassin au cours du temps est matérialisé par la position des biseaux appartenant à des groupes lithostratigraphiques successifs. L'épaisseur des dépôts varie de quelques dizaines de mètres dans la partie distale jurassienne à plus de 4000 m dans la partie proximale subalpine. Sur le plan lithostratigraphique, la Molasse peut être divisée en quatre groupes où les faciès prédominants sont alternativement marins et terrestres: UMM (Molasse marine inférieure, Rupélien-Chattien), USM (Molasse d'eau douce inférieure, Rupélien-Burdigalien?), OMM (Molasse marine supérieure, Burdigalien-Langhien?) et OSM (Molasse d'eau douce supérieure, LanghienSerravalien). Du nord-ouest au sud-est, le bassin molassique est divisé en trois ensembles tectoniques: i) la Molasse du Jura, ii) la Molasse du Plateau et iii) la Molasse subalpine. Par le biais d'une meilleure compréhension des processus qui contrôlent le régime paléogéothermique, l'objectif de cette étude est la reconstitution de l' histoire thermique de quelques périmètres du bassin molassique au cours du Tertiaire. La démarche suivie peut être décomposée en trois phases principales: - La phase d'échantillonnage. Afin de rendre les résultats obtenus les plus significatifs possibles, les échantillons ont été prélevés avec une large dispersion géographique. Du sud-ouest au nord-est, cinq régions ont été explorées: Haute-Savoie (Bornes, Plateau de Bornes, Bassin de Bellegarde, Bassin de Rumilly) et bassin genevois, Suisse occidentale (région entre le lac de Neuchâtel et le lac de Genève), région du lac de Thoune, Suisse orientale (région centrée autour du lac de Zürich), Suisse septentrionale (région située dans la prolongation des failles du fossé rhénan vers le sud, dans le Jura tabulaire et le Jura plissé); - La phase d'analyse. Quatre types de méthodes ont été utilisées: étude de la réflectance de la vitrinite, étude diffractométrique des argiles, étude des inclusions fluides et pyrolyse RockEva!. - La cartographie des résultats et la modélisation de l'histoire thermique.