Магистерская диссертация посвящена разработке информационно-моделирующей системы зажигательного горна агломерационной машины. Результатом работы является проектирование и программная реализация информационно-моделирующей системы зажигательного горна агломерационной машины. В ходе работы произведен анализ и формализация существующей методики расчета конструкции зажигательного горна, на основе которого был реализован проект создания информационно-моделирующей системы. Созданная в результате работы система позволяет проводить расчеты агломерационной шихты, горения твердого топлива, горения природного газа, периодов зажигания, а также выбор горелочных устройств и обоснования высоты горна. Предусмотрен вывод основных расчетных показателей в табличном виде с возможностью настройки отдельных показателей и предварительного просмотра отчета. Использование разработанной информационной системы позволяет существенно сократить временные затраты, повысить эффективность процессов проектирования новых и анализа эффективности существующих конструкций зажигательного горна агломерационных машин. / The master's thesis is devoted to the development of an information-modeling system of an incendiary hearth of an agglomeration machine. The result of the work is the design and software implementation of the information-modeling system of the incendiary furnace of the sinter machine. In the course of the work, an analysis and formalization of the existing methodology for calculating the design of the incendiary hearth was made, on the basis of which the project of creating an information-modeling system was implemented. The system created as a result of the work makes it possible to carry out calculations of the sinter charge, solid fuel combustion, natural gas combustion, ignition periods, as well as the choice of burner devices and justification of the height of the hearth. The output of the main calculated indicators is provided in a table form with the ability to configure individual indicators and preview the report. Using the developed information system can significantly reduce time costs, increase the efficiency of new design processes and analyze the effectiveness of existing incendiary furnaces of sinter machines.

The European security order has for an extended period of time time rested on the assumption that interstate trade, and other economic ties, will lower the incentives for conflict initiation and thereby result in peace. This assumption was called into question on February 24, 2022, by the Russian re-invasion of Ukraine. Germany, as one of Europe’s primary proponents of interdependence, especially in its trade relationship to Russia defined by the pipeline natural gas, spirals into an energy crisis. How did it come to this? This thesis is an exploration of the concept of interdependence and its theoretical framework. Using congruence method, this thesis maps the internal processes of the concept, through two pieces of seminal research on interdependence theory – Robert O. Keohane & Joseph S. Nye’s Power and Interdependence and Dale C. Copeland’s Economic Interdependence and War – and their respective ability to comprehend the case of Russo-German gas relations. The results show that the two theoretical interpretations can, although not with equal strength, to a certain degree predict the outcome of the Russo-German case. In spite of this, the theories struggle to capture the existence of regional conflict, and the slight contradiction that the Russo-German relationship continued to deepen after the Russian annexation of Crimea in 2014.

The exigent need to address climate change and its adverse effects is felt all around the world. As pioneers in tackling carbon emissions, the European Union continue to be head and shoulders above other continents by implementing policies and keeping a tab on its carbon dependence and emissions. However, being one of the largest importers of Natural Gas in the world, the EU remains dependent on a fossil fuel to meet its demands.  The aim of the research is to investigate the barriers and constraints in the EU policies and framework that affects the natural gas decarbonization and to investigate the levelized cost of hydrogen production (LCOH) that would be used to decarbonize the natural gas sector. Thus a comprehensive study, based on existing academic and scientific literature, EU policies, framework and regulations pertinent to Natural gas and a techno economic analysis of possible substitution of natural gas with Hydrogen, is performed. The motivation behind choosing hydrogen is based on various research studies that indicate the importance and ability to replace to natural gas. In addition, Portugal provides a great environment for cheap green hydrogen production and thus chosen as the main region of evaluation.  The study evaluates the current framework based on a SWOT ((Strength, Weakness, and Opportunities & Weakness) analysis, which includes a PESTEL (Political, Economic, Social, Technological, Environmental & Legal) macroeconomic factor assessment and an expert elicitation. The levelized cost of hydrogen is calculated for blue (SMR - Steam Methane Reforming with natural gas as the feedstock) and green hydrogen (Electrolyzer with electricity from grid, solar and wind sources). The costs were specific to Portuguese conditions and for the years 2020, 2030 and 2050 based on availability of data and the alignment with the National Energy and Climate Plan (NECP) and the climate action framework 2050. The sizes of Electrolyzers are based on the current Market capacities while SMR is capped at 300MW. The thesis only considers production of hydrogen. Transmission, distribution and storage of hydrogen are beyond the scope of the analysis.  Results show that the barriers are mainly related to costs competitiveness, amendments in rules/regulations, provisions of incentives, and constraints in the creation of market demand for low carbon gases. Ensuring energy security and supply while being economically feasible demands immediate amendments to the regulations and policies such as incentivizing supply, creating a demand for low carbon gases and taxation on carbon.  Considering the LCOH, the cheapest production costs continue to be dominated by blue hydrogen (1.33 € per kg of H2) in comparison to green hydrogen (4.27 and 3.68 € per kg of H2) from grid electricity and solar power respectively. The sensitivity analysis shows the importance of investments costs and the efficiency in case of electrolyzers and the carbon tax in the case of SMR. With improvements in electrolyzer technologies and increased carbon tax, the uptake of green hydrogen would be easier, ensuring a fair yet competitive gas market. / Det starka behovet av att ta itu med klimatförändringarna och deras negativa effekter är omfattande världen över. Den europeiska unionen utgör en pionjär när det gäller att såväl hantera sina koldioxidberoende och utsläpp som att implementera reglerande miljöpolitik, och framstår därmed som överlägsen andra stater och organisationer i detta hänseende. Unionen är emellertid fortfarande mycket beroende av fossilt bränsle för att uppfylla sina energibehov, och kvarstår därför som en av världens största importörer av naturgas.  Syftet med denna forskningsavhandling är att undersöka befintliga hinder och restriktioner i EU: s politiska ramverk som medför konsekvenser avkolningen av naturgas, samt att undersöka de utjämnande kostnaderna för väteproduktion (LCOH) som kan användas för att avkolna naturgassektorn. Därmed utförs en omfattande studie baserad på befintlig akademisk och vetenskaplig litteratur, EU: s politiska ramverk och stadgar som är relevanta för naturgasindustrin. Dessutom genomförs en teknisk-ekonomisk analys av eventuella ersättningar av naturgas med väte. Valet av väte som forskningsobjekt motiveras olika forskningsstudier som indikerar vikten och förmågan att ersätta till naturgas. Till sist berör studien Portugal. som tillhandahåller en lämplig miljö för billig och grön vätgasproduktion. Av denna anledning är Portugal utvalt som den viktigaste utvärderingsregionen.  Studien utvärderar det nuvarande ramverket baserat på en SWOT-analys ((Strength, Weakness, and Opportunities & Weakness), som inkluderar en PESTEL (Political, Economical, Social, Technological, Environmental och Legal) makroekonomisk faktoranalys och elicitering. Den utjömnade vätekostnaden beräknades i blått (SMR - Ångmetanreformering med naturgas som råvara) och grönt väte (elektrolyser med el från elnät, sol och vindkällor). Kostnaderna var specifika för de portugisiska förhållandena under åren 2020, 2030 och 2050 baserat på tillgänglighet av data samt anpassningen till den nationella energi- och klimatplanen (NECP) och klimatåtgärdsramen 2050. Storleken på elektrolyserar baseras på den nuvarande marknadskapaciteten medan SMR är begränsad till 300 MW. Avhandlingen tar endast hänsyn till produktionen av vätgas. Transmission, distribution och lagring av väte ligger utanför analysens räckvidd.  Resultaten visar att hindren är främst relaterade till kostnadskonkurrens, förändringar i stadgar och bestämmelser, incitament och begränsningar i formerandet av efterfrågan på koldioxidsnåla gaser på marknaden. Att säkerställa energiförsörjning och tillgång på ett ekonomiskt hållbart sätt kräver omedelbara ändringar av reglerna och politiken, såsom att stimulera utbudet, att skapa en efterfrågan på koldioxidsnåla gaser och genom att beskatta kol.  När det gäller LCOH dominerar blåväte beträffande produktionskostnaderna (1,33 € per kg H2) jämfört med grönt väte (4,27 respektive 3,68 € per kg H2) från elnät respektive solenergi. Osäkerhetsanalysen visar vikten av investeringskostnader och effektiviteten vid elektrolysörer och koldioxidskatten för SMR. Med förbättringar av elektrolys-tekniken och ökad koldioxidskatt skulle upptagningen av grön vätgas vara enklare och säkerställa en rättvis men konkurrenskraftig gasmarknad.

[pt] No Brasil, a demanda de gás natural possui um comportamento estocástico devido ao consumo das usinas termelétricas, as quais operam em regime de complementariedade ao sistema hidrelétrico. O suprimento de gás natural para estas usinas depende em grande parte do fornecimento de Gás Natural Liquefeito (GNL) spot, importado através de navios metaneiros. Em função do tempo de trânsito dos navios, as compras de GNL devem ocorrer com antecedência em relação ao despacho hidrotérmico. Este descasamento de tempo incentiva a utilização de mecanismos de compatibilização da dinâmica do setor elétrico com a dinâmica da cadeia do gás natural. Uma possibilidade de aumentar a sinergia entre estes domínios é utilizar uma estocagem de gás natural para inserir flexibilidade no sistema. A viabilidade da estocagem dependerá do preço do gás e da demanda ao longo do horizonte de análise. O objetivo deste trabalho é a construção de um modelo de programação linear para dimensionar a capacidade de uma estocagem de gás natural sob incerteza de demanda e de preço de GNL. O modelo apresentado é um híbrido de otimização estocástica, construído para considerar a incerteza do consumo de gás, com otimização robusta, construído para levar em conta a incerteza relacionada aos preços do GNL. O modelo caracteriza o perfil de risco do supridor de gás natural pela utilização do Conditional Value-at-Risk (CVaR) e utiliza um critério de segurança que reproduz um processo de suprimento avesso a risco de déficit. Ao final do trabalho é apresentado um estudo de caso hipotético, utilizando dados públicos do setor elétrico e de gás natural, para avaliar a implantação da estocagem para 2.000 cenários de demanda e patamares distintos de robustez à variação do preço do GNL. / [en] In Brazil, natural gas demand has stochastic behavior since gas-fired power plants operate in conjunction with the hydroelectric system. Natural gas supply to these plants relies upon Liquefied Natural Gas (LNG), imported through cryogenic ships. LNG acquisitions must occur before the natural gas demand is known because of the time of displacement of the ships. This lack of synchronism stimulates the use of harmonizing mechanisms between the electric sector and the natural gas sector. In this context, natural gas storage could be used to introduce flexibility into the system and increase synergy between natural gas supply and demand dynamics. However, the economic performance of the storage will depend on actual gas prices and demand behavior during the period of analysis. This study aims to construct a linear programming model to determine the size of a natural gas storage under demand and LNG price uncertainty. The model is a hybrid of a stochastic optimization algorithm – developed to consider gas demand uncertainty – and a robust optimization algorithm – built to take into account LNG price uncertainty. A convex combination between Conditional Value-at-Risk (CVaR) and expected value is also used to indicate the supplier risk profile as well as a security criterion, introduced to represent a deficit-averse supply process. At the end, a hypothetic case is presented to evaluate the implementation of a natural gas storage. The case presented uses public data from the Brazilian electric and gas natural sectors and considers 2.000 demand scenarios and various levels of robustness to LNG price variation.

Erdöl und Erdgas liegen als flüssige Kohlenwasserstoffe in porösen Sedimentgesteinen im geologischen Untergrund vor. Um diese Kohlenwasserstoffe zu gewinnen, wird der Untergrund durch Tiefbohrungen zur Förderung erschlossen. Anschließend erfolgt die Förderung des Erdöls in drei Phasen: der Primär-, Sekundär- und Tertiärförderung. In der primären Phase wird Erdöl durch den Druck in der Lagerstätte gewonnen, in der sekundären Phase durch künstliche Aufrechterhaltung des Drucks und in der tertiären Phase durch technische Beeinflussung der strömungsmechanischen und thermodynamischen Eigenschaften des Erdöls. Dennoch verbleibt insbesondere bei Schweröllagerstätten ein Anteil von 45 bis 90 % des ursprünglich in der Lagerstätte vorhandenen Erdöls in der Lagerstätte. Aufgrund strömungsmechanischer und thermodynamischer Einschränkungen ist eine Gewinnung dieses Anteils technisch und/oder wirtschaftlich nicht möglich. Meist wird die Lagerstätte nach Abschluss der Förderung verfüllt und die übertägigen Anlagen zurückgebaut. Zugleich steigt weltweit der Bedarf an Energiequellen, insbesondere an solchen, die für die Dekarbonisierung und Umstellung auf umweltschonende Energien benötigt werden. Wasserstoff wird voraussichtlich als chemischer Energieträger der zukünftige Schlüsselrohstoff für die Energiewende sein. Diese Forschungsarbeit untersucht die Weiternutzung bzw. Erschließung ausgeförderter Erdöllagerstätten zur Wasserstoffgewinnungmittels thermischer Verfahren. Diese Verfahren orientieren sich an bereits etablierten Methoden für die übertägige Verfahrenstechnik. Durch das Verfahren wird die Lagerstätte mithilfe der Verbrennung des in dieser vorhandenen Restöls erhitzt und das entstehende Koks durch eine Wasserinjektion in Synthesegas umzuwandeln. Durch die hohen Temperaturen entsteht in der Lagerstätte eine Atmosphäre aus Wasserdampf, die zur Vergasung des Kokses führt. Das Gas wird durch die Wasserfront aus der Lagerstätte in die Produktionsbohrungen verdrängt und kann anschließend an der Oberfläche aufbereitet werden. Im Kontext der Lagerstättenprozesse entsteht nicht nur Wasserstoff, sondern auch weitere Verbrennungsprodukte wie Kohlenstoffmonoxid, Kohlenstoffdioxid, Sauergase und Kohlenwasserstoffgase. Diese werden verfahrenstechnisch aufbereitet und dampfreformiert in den obertägigen Anlagen. Zur Erfüllung der Anforderungen an blauen Wasserstoff ist die Reinjektion von Kohlenstoffdioxid erforderlich. In der Dissertation wird ein numerisches Berechnungsschema eingeführt und ausführlich getestet, um die lagerstättentechnische Simulation der thermischen Wasserstoffgewinnung durchzuführen. Anhand von Modelllagerstätten werden mithilfe dieses Schemas relevante Prozessparameter ermittelt und für die Übertragung auf die konkrete Lagerstättensimulation aufbereitet. Das Verfahren zur Wasserstoffförderung wird an einer antiklinalen Lagerstätte mit geostatistischer Heterogenität simuliert. Die Ergebnisse werden zur weiteren Auswertung bezüglich Integritätsfragen, Übertageanlagen sowie wirtschaftlicher und strategischer Aspekte herangezogen.

Contexte : L’exposition professionnelle aux sous-produits de combustion est répandue et peut contribuer à l'étiologie du cancer du sein. Cette étude vise à estimer l’association entre l’exposition professionnelle à certains sous-produits de combustion et le risque postménopausique de cancer du sein. Méthodes : Cette étude cas-témoins populationnelle comprenait des femmes ménopausées âgées de 47-75 ans résidant à Montréal, Québec (2008-2011). Les cas incluaient 695 femmes ayant reçu un diagnostic cancer du sein malin et 608 témoins sélectionnés aléatoirement à partir de la Liste électorale du Québec, appariés aux cas en fréquence (groupes d'âge de 5 ans). L’information sur les facteurs de risque et l'historique professionnel a été recueillie par entrevue. Des hygiénistes industriels ont évalué l'exposition à 293 agents, dont six sous-produits de combustion. Le risque de cancer du sein associé à l'exposition professionnelle à certains sous-produits a été estimé, pour l'ensemble des tumeurs et leurs sous-types moléculaires, par régression logistique inconditionnelle avec rapports de cotes ajustés (RC) et intervalles de confiance à 95 % (IC 95%). Résultats : Des associations positives suggestives ont été trouvées entre l'exposition aux hydrocarbures aromatiques polycycliques et certains sous-types moléculaires de tumeurs : toutes tumeurs, RC=1,18 (IC95%=0,80-1,76), tumeurs luminales A, RC=1,25 (IC95%=0,81-1,93) et tumeurs luminales B, RC=2,09 (IC95%=0,87-4,60). Un risque élevé a été observé avec l'exposition aux fumées de cuisson pour les tumeurs HER2-enrichies (RC=2,63, IC95%=0,98-6,40). Conclusion : L'exposition à certains sous-produits de combustion peut augmenter le risque de certains sous-types moléculaires de cancer du sein. Des études futures explorant cette association sont justifiées. / Background: Postmenopausal breast cancer is the most common cancer among women, yet little is known about its association with occupational exposures. Exposure to combustion by-products is widespread in occupational settings and may contribute to breast cancer etiology. Here, we sought to estimate the association between lifetime occupational exposure to select combustion by-products and the risk of postmenopausal breast cancer. Methods: This population-based case-control study included postmenopausal women residing in Montreal, Quebec (2008-2011). Cases comprised 695 women aged 47-75 years diagnosed with incident malignant breast cancer, and 608 controls randomly selected from the Quebec Electoral List, frequency-matched to cases (5-year age groups). Information on risk factors and employment history was collected by interview. Exposure to 293 agents, including six combustion by-products was assessed by industrial hygienists. Unconditional logistic regression was used to estimate adjusted odds ratios (ORs) and 95% confidence intervals (95% CIs) for breast cancer risk, both overall and by tumor molecular subtypes, to occupational exposure to select combustion by-products. Results: We found suggestive positive associations between exposure to polycyclic aromatic hydrocarbons and certain molecular subtypes of tumors: for all tumors, OR=1.18 (95% CI: 0.80-1.76), Luminal A tumors, OR=1.25 (95% CI: 0.81-1.93) and Luminal B tumors, OR=2.09 (95% CI: 0.87-4.60). Elevated risked were observed for exposure to cooking fumes for HER2-enriched tumors (OR=2.63, 95% CI: 0.98-6.40). Conclusion: Exposure to select combustion by-products may increase the risk of certain hormonal subtypes of breast cancer. Future studies exploring this association are warranted.

This report travels through multiple disciplines to seek innovative and sustainable energy solutions for wastewater treatment plants. The first subject is a report about increased global temperatures and an over-exploitation of natural resources that threatens ecosystems worldwide. The situation is urgent where the current trend is a 2°C increase of global temperatures already in 2040. Furthermore, the energy-land nexus becomes increasingly apparent where the world is going from a dependence on easily accessible fossil resources to renewables limited by land allocation. A direction of the required transition is suggested where all actors of the society must contribute to quickly construct a new carbon-neutral resource and energy system. Wastewater treatment is as required today as it is in the future, but it may move towards a more emphasized role where resource management and energy recovery will be increasingly important. This report is a master’s thesis in energy engineering with an ambition to provide some clues, with a focus on energy, to how wastewater treatment plants can be successfully integrated within the future society. A background check is conducted in the cross section between science, society, politics and wastewater treatment. Above this, a layer of technological insights is applied, from where accessible energy pathways can be identified and evaluated. A not so distant step for wastewater treatment plants would be to absorb surplus renewable electricity and store it in chemical storage mediums, since biogas is already commonly produced and many times also refined to vehicle fuel. Such extra steps could be excellent ways of improving the integration of wastewater treatment plants into the society. New and innovative electric grid-connected energy storage technologies are required when large synchronous electric generators are being replaced by ‘smaller’ wind turbines and solar cells which are intermittent (variable) by nature. A transition of the society requires energy storages, balancing of electric grids, waste-resource utilization, energy efficiency measures etcetera… This interdisciplinary approach aims to identify relevant energy technologies for wastewater treatment plants that could represent decisive steps towards sustainability.

Trace component analysis in gasification processes are important part of elemental component balances in order to understand the fate of these participating compounds in the feedstock. Residual traces in the raw synthesis gas after quench could bring about the poisoning of catalysts and corrosion effects on plant facilities. The objective of this work is to investigate the effects of quenching operation on the trace components during test campaigns of the autothermal non-catalytic reforming of natural gas (Gas-POX) mode in the HP POX (high pressure partial oxidation) test plant. In order to achieve this, Aspen Plus simulation model of the quench chamber of the HP POX test plant was developed to re-calculate the quench chamber input amount of different trace compounds from their output amount measured during test points of the Gas-POX campaigns. Variation in quench water temperatures from 130 °C to 220 °C and pH value of quench water as well as the resulting variation in Henry´s and Dissociation constant of the traces (CO2, H2S, NH3 and HCN) changed the distribution of traces calculated in the quench water. The formation of traces of organic acid (formic acid and acetic acid) and traces of BTEX, PAHs and soot in the quench water effluent were discussed. The discrepancies between equilibrium constant and reaction quotient (non-equilibrium or real) for the formation of NH3 and HCN at the exit of the gasifier were discussed. The assessment of the results in this work should lead to the improvement in the understanding of trace components and concepts that could be employed to influence their formation and reduction.

<p>The present work is focused on the synthesis of small-scale (modular processes) to produce olefins from light alkane resources in shale gas.</p> <p>Olefins, which are widely used to produce important chemicals and everyday consumer products, can be produced from light alkanes - ethane, propane, butanes etc. Shale gas is comprised of light alkanes in significant proportion; and is available in abundance. Meanwhile, shale gas wells are small sized in nature and are distributed over many different areas or regions. In this regard, using shale gas as raw material for olefin production would require expensive transportation infrastructure to move the gas from the wells or local gas gathering stations to large central processing facilities. This is because existing technologies for natural gas conversions are particularly suited for large-scale processing. One possible way to take advantage of the abundance of shale resource for olefins production is to place small-sized or modular processing plants at the well sites or local gas gathering stations.</p> <p>In this work, new process concepts are synthesized and studied towards developing simple technologies for on-site and modular processing of light alkane resources in shale gas for olefin production. Replacing steam with methane as diluent in conventional thermal cracking processes is proposed to eliminate front-end separation of methane from the shale gas processing scheme. Results from modeling studies showed that this is a promising approach. To eliminate the huge firebox volume associated with thermal cracking furnaces and allow for a compact cracking reactor system, the use of electricity to supply heat to the cracking reactor is considered. Synthesis efforts led to the development of two electrically powered reactor configurations that have improved energy efficiency and reduced carbon footprints over and compare to conventional thermal cracking furnace configurations.</p> <p>The ideas and results in the present work are radical in nature and could lead to a transformation in the utilization of light alkanes, natural gas and shale resources for the commercial production of fuels and chemicals.</p>

Trace component analysis in gasification processes are important part of elemental component balances in order to understand the fate of these participating compounds in the feedstock. Residual traces in the raw synthesis gas after quench could bring about the poisoning of catalysts and corrosion effects on plant facilities. The objective of this work is to investigate the effects of quenching operation on the trace components during test campaigns of the autothermal non-catalytic reforming of natural gas (Gas-POX) mode in the HP POX (high pressure partial oxidation) test plant. In order to achieve this, Aspen Plus simulation model of the quench chamber of the HP POX test plant was developed to re-calculate the quench chamber input amount of different trace compounds from their output amount measured during test points of the Gas-POX campaigns. Variation in quench water temperatures from 130 °C to 220 °C and pH value of quench water as well as the resulting variation in Henry´s and Dissociation constant of the traces (CO2, H2S, NH3 and HCN) changed the distribution of traces calculated in the quench water. The formation of traces of organic acid (formic acid and acetic acid) and traces of BTEX, PAHs and soot in the quench water effluent were discussed. The discrepancies between equilibrium constant and reaction quotient (non-equilibrium or real) for the formation of NH3 and HCN at the exit of the gasifier were discussed. The assessment of the results in this work should lead to the improvement in the understanding of trace components and concepts that could be employed to influence their formation and reduction.:List of Figures vii List of Tables xii List of Abbreviations and Symbols xiii 1 Introduction 1 1.1 Background 1 1.2 Objective of the Work 4 1.3 Overview of the Work 5 2 Process and test conditions 6 2.1 HP POX test plant 6 2.2 Test campaign procedure 8 2.2.1 Gas-POX operating parameter range 8 2.2.2 Gas-POX experiments 9 2.2.3 Net reactions of partial oxidation 9 2.3 Gaseous feedstock characterization 11 2.3.1 Natural gas feedstock composition 11 2.4 Analytical methods for gaseous products 12 2.4.1 Hot gas sampling 12 2.4.2 Raw synthesis gas analysis after quench 13 2.5 Aqueous phase product analysis 14 2.5.1 Molecularly dissolved trace compounds and their ions trace analysis 14 2.5.2 Other trace analysis 15 2.6 Limit of accuracy in measurement systems 15 2.7 Summary 17 3 Simulation and methods 18 3.1 Test points calculation of the HP POX test campaign 18 3.1.1 Aspen Plus model for HP POX quench water system 19 3.2 Gas-POX 201 VP1 quench water system model simulation by Aspen Plus 23 3.2.1 Measured and calculated input parameters 23 3.2.2 Calculated sensitivity studies of species and their distribution for test point (VP1) 24 3.3 Used calculation tools related to the work 25 3.3.1 VBA in Excel 25 3.3.2 Python as interface between Aspen Plus and Microsoft Excel 26 3.3.3 Aspen Simulation Workbook 27 3.4 Summary 29 4 Trace components in quench water system 30 4.1 Physico-chemical parameters of quench water 31 4.1.1 Quench water pH adjustment 32 4.1.2 Henry constant 34 4.1.3 Dissociation constant 35 4.1.4 Organic acids in quench water 38 4.2 Carbon dioxide (CO2) 39 4.2.1 Results of sensitivity study: quench water temperature variation effects on CO2 41 4.2.2 Results of sensitivity study: quench water pH variation influence on CO2 42 4.3 Nitrogen compounds 43 4.3.1 Ammonia (NH3) 44 4.3.2 Results of sensitivity study: quench water temperature variation effects on NH3 46 4.3.3 Results of sensitivity study: quench water pH variation influence on NH3 47 4.3.4 Hydrogen Cyanide (HCN) 48 4.3.5 Results of sensitivity study: quench water temperature variation effects on HCN 50 4.3.6 Results of sensitivity study: quench water pH variation influence on HCN 50 4.4 Sulphur compounds: H2S 51 4.4.1 Results of sensitivity study: quench water temperature variation effects on H2S 53 4.4.2 Results of sensitivity study: quench water pH variation influence on H2S 54 4.5 Summary 55 5 Organic acids trace studies in quench water 57 5.1 Organic acids interaction with ammonia compounds in the quench water 57 5.2 Formic acid 62 5.2.1 Trace of formic acid in quench water 64 5.3 Acetic acid 67 5.3.1 Trace of acetic acid in quench water 69 5.4 Summary 72 6 Temperature approach studies for NH3 and HCN formation in gasifier 74 6.1 Nitrogen compounds: NH3 and HCN 74 6.2 Ammonia (NH3) formation in the gasifer 77 6.3 Hydrogen cyanide (HCN) formation in the gasifier 79 6.4 Discrepancies between back-calculated reaction quotients and equilibrium constants of the NH3 formation 81 6.4.1 Case 1: calculated equilibrium distribution between N2, NH3 and HCN 81 6.4.2 Case 2: calculated equilibrium distribution between NH3 and HCN 83 6.5 Summary 84 7 Traces of BTEX, PAHs and soot in quench water 86 7.1 Quench water behaviour 87 7.2 BTEX compounds 88 7.2.1 BTEX in quench water effluent 90 7.3 PAH compounds 93 7.3.1 PAHs in quench water effluent 95 7.4 Soot formation 99 7.4.1 Soots in quench water effluent 101 7.5 Summary 102 8 Summary and outlook 103 Bibliography 106 9 Appendix 135 List of Figures Figure 2.1: HP POX test plant main facility components and material flow courtesy of [Lurgi GmbH, 2008] 6 Figure 2.2: Simplified scheme of HP POX plant (including quench system) [Lurgi GmbH, 2008] 7 Figure 2.3: Overview of reactions of methane 10 Figure 3.1: Simplified scheme for HP POX quench water system 18 Figure 3.2: Aspen Plus flow diagrams of simulated HP POX quench water system 19 Figure 3.3: Integration of information and functions in VBA via Microsoft Excel to Aspen Plus model 25 Figure 3.4: Integration of information and functions in Python via Microsoft Excel to Aspen Plus model 26 Figure 3.5: ASW enables Excel users to rapidly run scenarios using the underlying rigorous models to analyze plant data, monitor performance, and make better decisions. 27 Figure 4.1: Vapour-liquid equilibria system of CO2, H2S, NH3, HCN and organic acids in the quench water and extended mechanisms according to [Kamps et al., 2001], [Alvaro et al., 2000], [Kuranov et al., 1996], [Xia et al., 1999] and [Edwards et al., 1978]. 30 Figure 4.2: HP POX quench water system with pH regulator for sensitivity studies 34 Figure 4.3: Henry´s constant for CO2, H2S, NH3 and HCN derived from [Edwards et al., 1978] for CO2, [Alvaro et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN 35 Figure 4.4: Dissociation constants for CO2, H2S, NH3, HCN and H2O derived from [Alvaro et al., 2000], [Kamps et al., 2001], and [Edwards et al., 1978] 37 Figure 4.5: The flow of CO2 in the quench water cycle (test point VP1). 40 Figure 4.6: Calculated quench water temperature variation and effects on CO2 distribution 42 Figure 4.7: Calculated influence of pH regulation and effects on CO2 distribution 43 Figure 4.8: The flow of NH3 in the quench water cycle (test point VP1). 46 Figure 4.9: Calculated quench water temperature variation and effects on NH3 distribution 47 Figure 4.10: Calculated influence of pH regulation and effects on NH3 distribution 48 Figure 4.11: The flow of HCN in the quench water cycle (test point VP1). 49 Figure 4.12: Calculated quench water temperature variation and effects on HCN distribution 50 Figure 4.13: Calculated influence of pH regulation and effects on HCN distribution 51 Figure 4.14: The flow of H2S in the quench water cycle (test point VP1) 53 Figure 4.15: Calculated quench water temperature variation and effects on H2S distribution 54 Figure 4.16: Calculated influence of pH regulation and effects on H2S distribution 55 Figure 5.1: Aspen Plus back-calculated (real) formic acid concentration, quench water temperature and the calculated equilibrium formic acid concentration against back-calculated (real) ammonia concentration for the 47 test points (using amongst others sampled HCOO- and NH4+ values according to Table 2.6). 59 Figure 5.2: Aspen plus back-calculated (real) formic acid concentration, back-calculated (real) ammonia concentration and the calculated equilibrium formic acid concentration against quench water temperature for the 47 test points (using amongst others sampled HCOO- and NH4+ values according to Table 2.6). 60 Figure 5.3: Aspen plus back-calculated (real) acetic acid concentration, quench water temperature and the calculated equilibrium acetic acid concentration against back-calculated (real) ammonia concentration for the 47 test points. 61 Figure 5.4: Aspen plus back-calculated (real) acetic acid concentration, back-calculated (real) ammonia concentration and the calculated equilibrium acetic acid concentration against quench water temperature for the 47 test points. 62 Figure 5.5: Concentration of formic acid (Aspen plus calculated m_eq and back-calculted m_real) formation in the quench and quench water temperature for the 47 test points. 64 Figure 5.6: Concentration of formic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench against quench water temperature for the 47 test points (as in Fig.5.2). 65 Figure 5.7: Comparison between formic acid equilibrium constant (Keq), reaction quotient (Kreal) and the quench water temperature for the 47 test points. 66 Figure 5.8: Comparison between formic acid equilibrium constant (Keq) and reaction quotient (Kreal) against quench water temperatures for the 47 test points. 67 Figure 5.9: Concentration of acetic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench and quench water temperature for the 47 test points. 69 Figure 5.10: Concentration of acetic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench against quench water temperature for the 47 test points (as in Fig.5.4). 70 Figure 5.11: Comparison between acetic acid equilibrium constant (Keq), reaction quotient (Kreal) and the quench water temperature for the 47 test points. 71 Figure 5.12: Comparison between acetic acid equilibrium constant (Keq) and reaction quotient (Kreal) against quench water temperatures for the 47 test points. 72 Figure 6.1: Mole fraction of gas compoents in the hot gas outlet out of gasifier against hot gas temperature for the 47 test points 76 Figure 6.2: Calculated reaction quotient (Q) and equlibrium constant (Keq) for NH3 against hot gas temperature for the 47 test points (see Fig. 9.10 in Appendix) 77 Figure 6.3: NH3 temperature approach against hot gas temperature for the 47 test points (see Fig. 9.11 in Appendix) 78 Figure 6.4: Calculated reaction quotient (Q) and equlibrium constant (Keq) for HCN against hot gas temperature for the 47 test points (see Fig. 9.13 in Appendix) 79 Figure 6.5: HCN temperature approach against hot gas temperature for the 47 test points (see Fig. 9.14 in Appendix) 80 Figure 6.6: Comparison between calculated real and equilibrium hot gas N2, NH3 and HCN mol fractions against their respective hot gas temperature (case 1). 82 Figure 6.7: Relations between back-calculated real and equilibrium hot gas N2, NH3 and HCN mol fractions (for chemical equilibrium according to equations (6.1) and (6.4)) against their respective hot gas temperature (see Case 1, Section 6.4.1, and Fig. 6.6) 82 Figure 6.8: Comparison between calculated real and equilibrium hot gas HCN mol fraction against their respective hot gas temperature (case 2). 83 Figure 6.9: Relations between back-calculated real and equilibrium hot gas HCN mol fractions, and change in NH3 mol fractions (for chemical equilibrium according to equation (6.4)), against their respective hot gas temperature (see. Case 2, Section 6.4.2 and Fig. 6.7) 84 Figure 6.10 Comparison between NH3 and HCN formation (mole fraction) calculated equilibrium constant (Keq) and calculated reaction quotient (Q), N2 consumption and hot gas temperatures for the 47 test points (case 1 and case 2). 85 Figure 7.1: HP POX test plant quench water system 88 Figure 7.2: Traces of BTEX measured in the Gas-POX 203 – 207 quench water effluent sample. 91 Figure 7.3: Individual component of BTEX measured in the Gas-POX 203 – 207 quench water effluent sample. 92 Figure 7.4: (a) Alkyl radical decomposition and (b) C1 and C2 hydrocarbons oxidation mechanism [Warnatz et al., 2000] 93 Figure 7.5: Recombination of C3H3 to form benzene 94 Figure 7.6: The Diels - Alder reaction for the formation of PAHs 95 Figure 7.7: Amount of PAHs that were detected in Gas-POX 203 – 207 test points quench water effluent samples. 97 Figure 7.8: Distribution of PAH compounds in Gas-POX 203 – 207 quench water effluent samples. 98 Figure 7.9: Some steps in soot formation [McEnally et al., 2006]. 99 Figure 7.10: Illustration of soot formation path in homogenous mixture [Bockhorn et al., 1994] 100 Figure 9.1: Aspen flow sheet set up for HP POX quench system GasPOX 201 VP1 (simplified and extension of Fig. 3.2, organic acids not taken into account). Tabulated values are given in Table 9.11. 135 Figure 9.2: Comparison between the Henry´s constant profiles: Aspen Plus (markers) and Literatures (solid lines) ([Edwards et al., 1978] for CO2, [Alvaro et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN as it can be seen in Fig. 4.3) 137 Figure 9.3: Henry´s constant profiles derived from literatures ([Edwards et al., 1978] for CO2, [Alvaro Pérez-Salado et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN as it can be seen in Fig. 4.3) 137 Figure 9.4: Comparison between the dissociation constant profiles: Aspen Plus (markers) and Literatures (solid or dashed lines) [Alvaro et al., 2000], [Kamps et al., 2001], and [Edwards et al., 1978] as in Fig.4.4. 138 Figure 9.5: Dissociation constant profiles derived from literatures [Kamps et al., 2001], and [Edwards et al., 1978] as in Fig.4.4. 138 Figure 9.6: Calculated pH values, temperature range and species 139 Figure 9.7: Aspen Plus flow sheet setup for organic acid compounds calculations (GasPOX 201 VP1, see also Table 9.12) 142 Figure 9.8: Aspen Plus flow sheet setup for nitrogen compounds calculations (GasPOX 201 VP1, see also Table 9.12, organic acids are taken into account in the aqueous streams of the quench system) 145 Figure 9.9: Yield of ammonia in gasifier (calculated real) and hot gas temperature against the 47 test points 146 Figure 9.10: Kreal or reaction quotient for ammonia formation in the gasifier against the 47 test points. 146 Figure 9.11: Temperature approach studies for ammonia and the 47 test points 147 Figure 9.12: Yield of HCN from the gasifier (calculated real and equilibrium) and hot gas temperature and the 47 test points 147 Figure 9.13: Comparison between equilibrium constant and reaction quotient for HCN and 47 test points 148 Figure 9.14: Temperature approach studies for HCN and the 47 test points 148 Figure 9.15: Comparison among equilibrium constants of reactions against temperature, T [°C] 149 Figure 9.16: Comparison among equilibrium constants of reactions against temperature, 1/T [1/K] 150 List of Tables Table 2.1: Outline of Gas-POX mode operating parameter range 8 Table 2.2: Outline of test runs operating mode and parameters of chosen test campaigns 9 Table 2.3: Natural gas feedstock compositions 12 Table 2.4: Product synthesis gas analysis method (hot gas before quench) [Brüggemann, 2010] 12 Table 2.5: Analysis methods for raw synthesis gas [Brüggemann, 2010] 13 Table 2.6: Analysis methods for aqueous phase products [Brüggemann, 2010] 14 Table 2.7: Relative accuracy for the measured value for temperature, pressure and flow of each feed and product stream [Meyer, 2007] and [Brüggemann, 2010] 17 Table 3.1: Description of blocks used in Aspen Plus simulation. 20 Table 3.2: HP POX test plant quench water cycle parameters Gas-POX 201 VP1* 23 Table 3.3: pH regulator parameters 24 Table 4.1: Organic acids distribution in streams for VP1 based on calculation from Aspen Plus. 38 Table 4.2: The distribution of CO2 and its ions in all the streams 40 Table 4.3: The distribution of NH3 and its ions in all the streams 45 Table 4.4: The distribution of HCN and its ions in all the streams 49 Table 4.5: The distribution of H2S and its ions in all the streams 52 Table 7.1: Relative sooting tendency [Tesner et al., 2010] 101 Table 9.1: Natural gas feed analysis method [Brüggemann, 2010] 135 Table 9.2: pH scale with examples of solution [NALCO 2008] 136 Table 9.3: Gas-POX test campaigns and with designated serial numbers 140 Table 9.4: Summary of correlation coefficient (r) from Figures in Chapter 5 144 Table 9.5: Comparison among reactions temperatures and heat of reactions 149 Table 9.6: Content of BTEX compounds in Gas-POX quench water samples 151 Table 9.7: BTEX in quench water effluent samples results 152 Table 9.8: Content of PAH compounds in Gas-POX quench water samples 157 Table 9.9: PAHs in quench water effluent samples results 160 Table 9.10: Soot in quench water effluent samples results 169 Table 9.11: Aspen Plus flow sheet setup stream details (GasPOX 201 VP1, according to Fig.3.2 and Fig.9.1, organic acids not taken into account) 170 Table 9.12: Aspen Plus flow sheet setup for organic acid and nitrogen compounds calculations for GasPOX 201 VP1 (according to Figures 9.7 and 9.8, organic acids are taken into account) 174