Intimate knowledge of ammonia fueling gas turbines is of crucial importance for power generation sectors, owing to its carbon-free nature and high hydrogen capacity. Anticipated challenges include, among others, the difficulty to stabilize ammonia flames and on top of that the propensity of ammonia flames to produce large quantities of nitrogen monoxide emissions. In gas turbine devices, combustion in practice occurs in a turbulent swirl flow and at elevated pressure conditions. The stability of ammonia flames and the production of NO emissions are sensitive to such parameters. This body of work focuses on the development of a swirl combustor, ~30kW thermal power, for investigating behaviors of flame stability limits and NO emissions from the combustion of ammonia fuel with mixtures of hydrogen or methane at pressure conditions up to 5 bar. Data show that increasing the ammonia addition increases the equivalence ratio at the lean blowout limit but also reduces the flames’ propensity to flashback. If the volume fraction of ammonia in the fuel blend exceeds a critical value, increasing the equivalence ratio at a fixed bulk velocity does not yield flashback and rich blow-out occurs instead. This significantly widens the range of equivalence ratios yielding stable ammonia flames. Regardless of the fuel blend, increasing the pressure increases the propensity to flashback if the bulk velocity remains constant. Pure ammonia-air flames are stable under elevated pressures, and the stable range of equivalence ratio becomes wider as the pressure increases. The NO emissions are measured for large ranges of equivalence ratios, ammonia fractions, and pressures. Regardless of the ammonia fraction, data show that competitively low NO emissions can be found for slightly rich equivalence ratios. Good NO performance is also found for very lean ammonia-hydrogen-air mixtures, regardless of the pressure. NO mole fractions for lean ammonia mixtures can be reduced as pressure increases, demonstrating the strong potential of fueling gas turbines with ammonia-hydrogen mixtures.

The utilization of ammonia as a fuel is a pragmatic approach to pave the way towards a low-carbon economy. Ammonia compromises almost 18 % of hydrogen by mass and accepted as one of the hydrogen combustion enablers with existing infrastructure for transportation and storage. From an environmental and sustainability standpoint, ammonia combustion is an attractive energy source with zero carbon dioxide emissions. However, from a practical point of view, the direct combustion of ammonia is not feasible due to the low reactive nature of ammonia. Due to the low combustion intensity, and the higher nitrogen oxide emission, ammonia was not fully investigated and there is still a lack of fundamental knowledge of ammonia combustion. In this thesis, the computational study of ammonia premixed flame characteristics under various hydrogen addition ratios and moderate or intense low oxygen dilution (MILD) conditions were investigated. Particularly, the heat release characteristics and dominant reaction pathways were analyzed. The analysis revealed that the peak of heat release for ammonia flame occurs near burned gas, which raises a question regarding the physics of this. Further analysis identified the dominant reaction pathways and the intermediate species (NH2 and OH), which are mainly produced in the downstream and back diffused to the leading edge and produce some heat in the low-temperature zone. To overcome low reactivity and poor combustion performance of pure ammonia mixture, the onboard ammonia decomposition to hydrogen and nitrogen followed by blending ammonia with hydrogen is a feasible approach to improve ammonia combustion intensity. With increasing hydrogen amount in the mixture, the enhancement of heat release occurs due to both transport and chemical effect of hydrogen. Another approach to mitigate the low reactive nature of ammonia may be eliminated by applying the promising combustion concept known as MILD combustion. The heat release characteristics and flame marker of ammonia turbulent premixed MILD combustion were investigated. The high fidelity numerical simulation was performed to answer fundamental questions of ammonia turbulent premixed combustion characteristics.

No description available.

The fact that hydrogen is a clean and versatile fuel offers an attractive carbon-free source of energy and leverages the U.S. economy toward long-term sustainable economic growth. At an industrial scale, hydrogen production is mostly relying on methane steam reforming producing stoichiometric amounts of carbon oxides (CO and CO2), which imposes economic and environmental concerns. To mitigate the issue, we propose NH3 assisted anaerobic reforming of natural gas liquids (ethane and propane) as an alternative approach to produce COx free hydrogen. Here, in the first chapter, through comprehensive performance evaluation, characterization, and transient kinetic studies, it is shown that the atomically dispersed Re-oxo grafted into framework Al of the HZSM-5 zeolite are highly active and stable for the ammonia reforming of ethane and propane at temperatures comparable to steam reforming ≤ 650 °C. In the second chapter, an alternative non- noble Ni/Ga intermetallic compound (IMC) with various Ni to Ga ratios is synthesized through the solvothermal synthesis by forming the oxalate MOF precursor. The result indicates that while Ni-rich samples form pure Ni3Ga IMC with promising catalytic performance, the Ga rich catalyst consists of segregated phases of Ni/Ga IMC and Ga2O3 with ill-defined structure showing lower stability despite the high activity. In chapter 3, a bifunctional Ni/Ga supported ZSM-5 is successfully developed in ethane aromatization. Influence of metal function in early-stage and steady-state activity and stability as well as structure reactivity relation was investigated applying comprehensive characterization, performance test, deactivation modeling, and transient studies. The results suggest that a tandem reaction mechanism between Ni3Ga intermetallic compound, Ga cation, and Bronsted acid sites of zeolite is responsible for the superior performance of bimetallic catalysts compared to their monometallic counterpart. In the last chapter, applying transient kinetic technique, the mechanism of ethane aromatization over Pt and Zn supported ZSM-5 model catalysts was precisely explored. The results reveal that despite mechanistic differences between these catalysts, ethane amortization on both catalysts follows a hydrocarbon pool mechanism.

In this work we present a carbon free gas diffusion electrode (GDE) design. It is a first step towards improvement of technologies like alkaline fuel cells, some alkaline electrolyzes and metal-air-batteries by circumventing carbon degradation. A nickel-mesh was made hydrophobic and subsequently electrochemically coated with MnOx as electrocatalyst. By this, a carbon free GDE was prepared. The contact angle, specific surface area (BET), pore size distribution, crystal phase (XRD) and electrochemical properties were determined. The deposition scan rate (rscan) during dynamic MnOx deposition altered the macro surface structure, pore size distribution and deposited mass. High catalyst masses with high specific surface area were achieved by lower rscan, but hydrophobicity was decreased. Impedance spectroscopy showed that higher MnOx mass will increase the ohmic resistance, because of the low conductivity of oxides, such as MnOx. The diffusion of dissolved oxygen is the major contributor to the total resistance. However, the polarization resistance was reduced by increased specific surface area of MnOx. It was concluded that the ORR and OER are limited by diffusion in this design but nevertheless showed reasonable activity for ±10 mA cm−2 corresponding to ∼8 Ω cm−2 while references exhibited ∼3.5 Ω cm−2 .

In present thesis, the fundamental studies on the reaction between MgO based refractories and slag were undertaken for the development of a carbon-free bonding MgO lining material. Alumina was selected as a potential binder material. Due to MgO-Al2O3 chemical reaction, the developed refractory was bonded by MgO·Al2O3 spinel phase. To begin with, an investigation of the dissolution process of dense MgO and MgO·Al2O3 spinel in liquid slag was carried out. To obtain reliable information for dissolution study, a new experimental method was therefore developed. In this method, a cylinder was rotating centrally in a special designed container with a quatrefoil profile. This method also showed a good reliability in revealing the dissolution mechanism by quenching the whole reaction system. The experimental results showed that the dissolution process of MgO and spinel was controlled by both mass transfer and chemical reaction. It was found that the rapid dissolution of spinel was mainly because of its larger driving force. To improve the resistance against slag penetration, two aspects were studied to develop carbon-free MgO refractory. First, colloidal alumina was used and the effect of its addition into MgO matrix was investigated. The use of colloidal alumina was to form bonding products in the grain boundary of MgO. The results showed that the alumina addition greatly improved the resistance of MgO based refractory against slag penetration in comparison with the decarburized MgO-carbon refractory. It was found that the improvement of resistance was mainly related to the spinel-slag reaction products of CaO·Al2O3 and CaO·MgO·Al2O3 solid phases at the grain boundaries. Second, the effect of particle size distribution on the penetration resistance of MgO was investigated. The most profound improvement against the slag penetration was obtained by using a proper particle size distribution. The results highlighted the importance of considering the refractory structure. Experiments were undertaken to investigate the dissolution mechanism of different types of MgO based refractories in liquid slag. It was observed that the dissolution of spinel bonded MgO refractory was much slower than the decarburized MgO-carbon refractory. The primary dissolution in spinel bonded MgO refractory occurred at the slag-penetrated layer, and the removal of this layer by peeling off enhanced the dissolution rate rapidly. / <p>QC 20170918</p> / European RFCS LEANSTORY project

Heat production together with electricity production stands for 31% of the global CO2 emissions. The production is as of today still highly dependent on fossil fuels, with a global district energy mix share of fossil fuels of 90%. To stay in line with the Paris Agreement, district heating must be configured away from fossil fuels by utilizing new emission free heat sources as well as creating higher energy efficient cities by incorporating more waste heat recovery. Helsinki has a District Heating (DH) dominated by fossil fuels and proclaimed goals of becoming carbon-­neutral by 2035, as of 2020 the annual heat demand in the city was 6.4TWh of heat. To do so, there is a need for research to investigate ways to include carbon-­free heat sources into the current heating system. There is currently a limited amount of literature available in this area and from the identified research gap the following main research question was developed. How can Helsinki achieve carbon-­free district heating? To easier answer the main research question, three three sub­questions were developed. (1) How large is the energy potential for non­-carbon based heat sources in Helsinki for district heating? (2) Where are the heat sources located? (3) What are the techno-­economic implications of the heat sources? A high resolution heat source mapping and spatial analysis was conducted for the city of Helsinki where low grade heat sources were to be identified for the purpose of district heating. The work focused on the following heat sources: Grocery Retail, Ice Rinks, Subway Stations, Data Centers, Wastewater, Sea Water Heat Pumps and Geothermal Energy. The developed model consists of five steps: (1) Heat source identification, (2) Technical potential evaluation, (3) DH-network mapping &amp; Spatial analysis, (4) Economic model, and (5) Techno-­Economic evaluation. A total of 363 heat source points was identified and evaluated. The combined results of the heat sources were a total capacity of 1257.56 MW with a resulting total annual heat production of 7008.31 GWh. The majority of the capacity and heat was contributed from seawater heat pumps and geothermal heat pumps. Around 84% of the mapped heat sources were within 100 meters of the current district heating piping network. The economical findings show that a majority of the heat sources yield a positive net present value and a discounted payback period of below 11 years. The levelized cost of heat was within reasonable expectations when compared to existing data where Data centers showed the most promising result. The study can conclude that Helsinki can potentially achieve a non-­carbon­ based district heating system with a sufficient heat production management strategy. / Värme­- och elproduktionen står tillsammans för 31% av de globala koldioxidutsläppen. Produktionen är idag fortfarande starkt beroende av fossila bränslen med en global andel fossila bränslen i fjärrvärmeblandningen på 90%. För att hålla sig i linje med Parisavtalet måste fjärrvärmen konfigureras bort från fossila bränslen genom att utnyttja nya utsläppsfria värmekällor samt skapa mer energieffektiva städer genom att utnyttja mer återvinning av spillvärme. Helsingfors har en fjärrvärme som domineras av fossila bränslen och har utsatt mål om att bli koldioxidneutralt senast 2035, vid 2020 hade staden en årlig värmekonsumption på 6.4 TWh. För att uppnå detta behövs forskning för att undersöka hur man kan inkludera koldioxidfria värmekällor i det nuvarande värmesystemet. Det finns för närvarande bristfällig mängd litteratur på detta område och utifrån den identifierade forskningsluckan utvecklades följande huvudsakliga forskningsfråga. Hur kan Helsingfors uppnå koldioxidfri fjärrvärme? För att lättare kunna besvara huvudfrågan utvecklades tre underfrågor. (1) Hur stor är energipotentialen för icke kolbaserade värmekällori Helsingfors för fjärrvärme? (2) Var finns värmekällorna? (3) Vilka är de tekno-­ekonomiska konsekvenserna av värmekällorna? En högupplöst kartläggning av värmekällor och en rumslig analys genomfördes för Helsingfors stad där lågkvalitativa värmekällor skulle identifieras för fjärrvärme. Arbetet fokuserade på följande värmekällor: Livsmedelsbutiker, isbanor, tunnelbanestationer, datacenter, avloppsvatten, värmepumpar för havsvatten och geotermisk energi. Den utvecklade modellen består av fem steg: (1) Identifiering av värmekällor, (2) Utvärdering av teknisk potential, (3) Kartläggning av DH­-nätverk och rumslig analys, (4) Ekonomisk modell och (5) Teknisk-ekonomisk utvärdering. Totalt 363 värmekällor identifierades och utvärderades. De kombinerade resultaten av värmekällorna var en total kapacitet på 1,257.56 MW med en total årlig värmeproduktion på 7,088.31 GWh. Merparten av kapaciteten och värmen kom från havsvattenvärmepumpar och geotermisk värme. Cirka 84% av de kartlagda värmekällorna låg inom 100 meter från det nuvarande fjärrvärmerörnätet. De ekonomiska resultaten visar att majoriteten av värmekällorna gav ett positivt nettonuvärde och en diskonterad återbetalningstid på mindre än 11 år. Den standardiserade kostnaden för värme låg inom rimliga gränser när den jämförs med befintliga data, där datacenter visade det mest lovande resultatet. Givet studiens resultat kan slutsatsen erhållas att Helsingfors potentiellt kan uppnå ett fossilfritt fjärrvärmesystem med en tillräcklig produktions-­ och värmehanteringsstrategi för fjärrvärme.

Under the current climate emergency, the electricity industry is taking quick steps to introduce new technology and market processes that could contribute to the decarbonization of the power system. The creation of the energy attribute certificates more than two decades ago has allowed consumers to choose the origin of their electricity. This market instrument has provided a new tool for tracking carbon-free electricity. It is how corporates can reduce their market-based emissions under the Scope 2 Green House Gas Protocol, a practice called annual matching of certificates. However, there are new trends in green electricity procurement that intend to improve the current system. These are called 24/7 carbon-free electricity and emissionality. To bring added value, these new methodologies require more granularity, hourly or less, for both electricity market data and energy attribute certificates. This can be achieved with so-called granular certificates. This thesis intends to provide some answers to the implications at a corporate level, specifically for their carbon accounting exercises, of adopting these practices. Different industrial and commercial electricity consumer profiles are analyzed in several European countries for 2021 under four different scenarios: base, RE100, 24/7, and emissionality. The results show that using hourly grid carbon intensity, location-based emission can differ from annual calculations up to 7%. In addition, it exemplifies some of the inefficiencies of the current practice of yearly matching of certificates. In 2021, it required less than 1% of a company’s total electricity sourcing costs to certify that they are 100 % renewable, acquiring mainly unbundled certificates. For the case of bundled certificates linked to a specific technology, these costs increased to 2,60 % for the case of the Dutch wind. The 24/7 scenario shows the actual coverage of the renewable contracted sources after the implementation of 24/7 carbon-free electricity matching, ranging from values between 48% and 99 %, depending on the consumption profile, the location, and the contracted renewable sources portfolio. Finally, the emissionality scenario provides the tools to determine where to locate new renewable generation capacity to decrease the emissions as much as possible. The results show that, under specific circumstances, these values can be three times higher. This thesis promotes adopting 24/7 carbon-free electricity practices for attributional carbon accounting methodologies. Nevertheless, its definition should be reviewed to easily include emissionality studies when new carbon-free renewable capacity construction comes from corporations’ green procurement decisions. / Under den rådande klimatkrisen vidtar elbranschen snabba åtgärder för att introducera ny teknik och nya marknadsprocesser som kan bidra till minskade koldioxitutsläpp från elsystemet. Införandet av energiattributcertifikat för mer än tjugo år sedan har gjort det möljigt för konsumenterna att välja vad de vill köpa för el. Detta marknadsinstrument har tillhandahållit ett nytt verktyg för att spåra koldioxidfri el. Det är så företag kan minska sina marknadsbaserade utsläpp enligt Scope 2 Green House Gas Protocol, en praxis som kallas årlig matchning av certifikat. Det finns dock nya trender inom upphandling av grön el som avser att förbättra det nuvarande systemet. Dessa kallas 24/7 koldioxidfri el och emissionalitet. För att skapa ett mervärde kräver dessa nya metoder en ökad granularitet, timbasis eller mindre, för både elmarknadsdata och energiattributcertifikat. Detta kan åstadkommas med så kallade granulära certifikat. Denna rapport avser att ge några svar på konsekvenserna på företagsnivå, specifikt för deras koldioxidredovisningar, av att anta dessa metoder. Olika industriella och kommersiella elkonsumentprofiler analyseras i flera europeiska länder för 2021 under fyra olika scenarier: bas, RE100, 24/7 och emissionalitet. Resultaten visar att då man använder koldioxidsintensitet för elnätet kan de platsberoende utsläppen skilja sig från de årliga beräkningarna med upp till 7%. Dessutom visas exempel på några av ineffektiviteterna i det nuvarande systemet med årlig matchning av certifikat. År 2021 krävdes det mindre än 1% av ett företags totala elkostnad för att intyga att de är 100% förnybara, huvudsakligen med separata certifikat. För paketerade certifikat kopplade till en specifik teknik ökade dessa kostnader till 2,60 % för fallet med holländska vindkraft. 24/7-scenariot visar att efter man implementerat 24/7 koldioxidfri elmatchning så varierar den faktiska täckningen av kontrakterad förnybar produktion mellan 48% och 99% beroende på förbrukningsprofil, lokalisering och vilka förnybara källor som kontrakterats. Slutligen tillhandahåller emissionalitetsscenariet verktygen för att bestämma var ny förnybar produktionskapacitet ska placeras för att minska koldioxidutsläppen så mycket som möjligt. Resultaten visar att under specifika omständigheter kan dessa värden vara tre gånger större. Det här examensarbetet främjar användningen av systemet för 24/7 koldioxidfri el för attributionella koldixodidredovisningsmetoder. Dess definition bör dock ses över för att enkelt inkludera emissionalitetsstudier då ny koldioxidfri av förnybar produktionskapacitet baserat på företags gröna upphandlingsbeslut.

Considering the growing importance of the electricity sector in the worldwide decarbonisation efforts, as well as large volumes of energy consumed by the commercial and industrial (C&amp;I) sector, corporate power procurement is found to be a significant contributor to building a net zero economy. Within this topic, hourly matching of carbon-free electricity supply with demand, or 24/7 Carbon-free Energy (24/7 CFE), is identified as a next-generation power procurement framework, with growing interest from a wide range of stakeholders in the energy sector and benefits backed by robust research evidence. This thesis focuses on analysing the potential impacts of 24/7 CFE on the C&amp;I consumers, as well as the wider system, in the context of the energy transition in the Netherlands, where some hourly matching initiatives already take place. The analysis is performed with the use of an existing open-source PyPSA model, with key elements of 24/7 CFE embedded in the code. The study finds that following the hourly matching strategy by the C&amp;I consumers has larger environmental benefits for both the user and the system, than the currently used approach. Furthermore, the price premium connected with following this ambitious framework can be significantly reduced, if advanced storage and clean generation technologies are developed. 24/7 Carbonfree Energy procurement can also complement more ambitious national decarbonisation goals, or EU-wide emission reduction mechanisms, such as the ETS. It also allows for hedging against various risks, for instance by building a generation portfolio independent from volatile natural gas prices, which is especially relevant in importing countries like the Netherlands. Finally, it is concluded that increased participation in 24/7 CFE strategies and cooperation between the private and public sector in developing technologies such as long-duration energy storage, Allam cycle or the hydrogen infrastructure, could accelerate the transition to a net zero electricity system in a cost-efficient manner. / Med tanke på den växande betydelsen av elsektorn i de globala ansträngningarna för att minska koldioxidutsläppen, såväl som stora volymer energi som förbrukas av den kommersiella och industriella (C&amp;I)-sektorn, har företagens kraftanskaffning visat sig vara en betydande bidragsgivare till att bygga en nettonollekonomi. Inom detta ämne identifieras timvis matchning av kolfri elförsörjning med efterfrågan, eller 24/7 Carbon-free Energy (24/7 CFE), som nästa generations ramverk för kraftanskaffning, med växande intresse från ett brett spektrum av intressenter inom energisektorn och fördelar som backas upp av robusta forskningsbevis. Den här avhandlingen fokuserar på att analysera de potentiella effekterna av 24/7 CFE på C&amp;I-konsumenter, såväl som det bredare systemet, i samband med energiomställningen i Nederländerna, där vissa timmatchningsinitiativ redan äger rum. Analysen utförs med användning av en befintlig PyPSA-modell med öppen källkod, med nyckelelement av 24/7 CFE inbäddade i koden. Studien visar att det att följa C&amp;I-konsumenternas timmatchningsstrategi har större miljöfördelar för både användaren och systemet än det för närvarande använda tillvägagångssättet. Dessutom kan prispåslaget i samband med att följa detta ambitiösa ramverk reduceras avsevärt om avancerad lagrings- och ren generationsteknik utvecklas. 24/7 Koldioxidfri energiupphandling kan också komplettera mer ambitiösa nationella utsläppsmål, eller EU-omfattande utsläppsminskningsmekanismer, såsom ETS. Det gör det också möjligt att skydda sig mot olika risker, till exempel genom att bygga en generationsportfölj oberoende av volatila naturgaspriser, vilket är särskilt relevant i importerande länder som Nederländerna. Slutligen dras slutsatsen att ökat deltagande i 24/7 CFE-strategier och samarbete mellan den privata och offentliga sektorn för att utveckla teknologier som långvarig energilagring, Allam-cykeln eller vätgasinfrastrukturen, skulle kunna påskynda övergången till ett netto-noll-elsystem på ett kostnadseffektivt sätt.

Urban neighborhoods that work toward carbon-free, climate-neutral goals, attain apositive energy balance, and aspire for excess renewable energy production aredefined as Positive Energy Districts (PEDs). PEDs are designed to contribute tosustainable urban growth, and it is also true that sustainable urban growth can leadto the creation of PEDs. Essentially, PEDs can be achieved by developing andfollowing sustainable infrastructure and urban planning practices including spatial,transportation, and social planning. As per JPI Urban Europe, the key aspects ofPEDs along with the funding include implementation strategies, stakeholders,climate transition, governance, legal frameworks, as well as technological andsystem innovation. As the name suggests, PED mainly comprises positive energy (energy management)and district (neighborhood) elements. The district aspect encompasses urbanplanning that constitutes strategic planning for sustainability implicationsconsisting of environmental, social, economical, mobility, andtransportation-related factors, all of which involve the users and its people. Thepositive energy aspect of a PED enables local energy production resulting in energyefficiency and potential cost savings for its residents. The thesis examines the performance of urban planning factors with the potential todevelop an existing neighborhood toward a PED. This research study explores theoverall sustainability of a neighborhood in terms of mobility, social, economic, andenvironmental factors. The performance of these factors is measured through KeyPerformance Indicators (KPIs), which measure the attributes of sustainability. Thesecontributing KPIs have been studied on a scale through a case study of HammarbySjöstad (HS) in Stockholm. The perception of stakeholders is collected for evaluatingKPIs. These KPIs have been thoroughly analyzed as designed during the planningstage and post-implementation to evaluate their success. The findings of this thesiscan be employed as guidelines for setting benchmarks and goals for the developmentof PEDs in cities throughout the world.