As economies advance towards decarbonization, industry follows suit. The ammonia (NH3) sector heavily relies on the energy- and carbon-intensive Haber-Bosch (HB) process, which accounts for nearly 2% of global CO2 emissions due to its reliance on fossil fuels. Emerging technologies are paving the way for fully renewable NH3 production, although the most mature green process still relies on the HB process, entirely replacing fossil fuels with electrolytic green hydrogen (H2). This work introduces the first developments towards the gradual incorporation of green H2 and air-separated nitrogen (N2) into a conventional NH3 production plant. Using Aspen Plus® V14 for modelling and simulation of Steam Methane Reforming (SMR), different scenarios incorporating 0 to 40 % of these alternative feedstocks were analyzed. An economic objective function is used in each scenario's optimization. To improve green H2 incorporation and ensure operational constraints were met, the simulations used an adapt... [more]

Recent geopolitical disruptions and extreme weather events have underscored the importance of resilience in global energy supply chains, particularly for import-dependent economies pursuing ambitious energy transition targets. These events have exposed the limitations of supply chain designs focused solely on cost minimization that lack the flexibility and redundancy required for secure operation under stress. As energy systems evolve toward higher shares of variable renewable energy and increased demand uncertainty, episodic manual re-planning becomes inadequate, highlighting the need for modeling frameworks that integrate predictive modeling, optimization, and control to enable intelligent and adaptive supply-chain design and operations under uncertainty. This work presents a comprehensive data-driven modeling and optimization framework for adaptive energy supply-chain networks under evolving demand. The framework integrates three layers: (i) a machine-learning model for demand forec... [more]

Replacing fossil resources with green hydrogen in industrial production holds tremendous potential for greenhouse gas mitigation. The economic feasibility and greenhouse gas (GHG) mitigation of grid-based electrolytic hydrogen production is highly dependent on the time-variant price and carbon footprint of electricity. In the present contribution, we analyse the economic feasibility of transitioning key carbon-intensive industries, steelmaking, and ammonia production, to green electrolytic hydrogen. Also, we investigate the competitiveness of green electrolytic hydrogen with other environmentally sustainable hydrogen sources derived from biomethane, biogas, and natural gas (associated with carbon capture and storage). We perform process design for steelmaking, ammonia production, and biogas-based steam reforming in order to determine key performance indicators such as costs, conversion factors, and GHG emissions. In particular, we allow for dynamic operation of the industrial processes... [more]

Methanol and ammonia are key energy carriers in a decarbonized society. This study assesses their use in power generation via two pathways: direct utilization as green fuels in fuel cells or as hydrogen carriers. Using these chemicals as hydrogen carriers achieves higher efficiencies (around 40%) due to the maturity of hydrogen fuel cells, resulting in electricity costs around 700 €/MWh compared to 1200 €/MWh for direct utilization. While hydrogen offers lower electricity production costs, efficiency advancements in methanol and ammonia fuel cells could enhance their competitiveness. Additionally, for scenarios involving transportation and power generation, methanol and ammonia prove economically viable, particularly for distances exceeding 3000 km. Consequently, both are crucial for addressing hydrogen-related challenges in the new renewable energy systems.

As initiatives to decarbonize societies increase, industry is also being considered for policies to encourage its sustainability. Ammonia (NH3) industry relies entirely on Haber-Bosch (HB) process, consuming fossil fuels for hydrogen production and energy purposes, accounting for more than 1 % of anthropogenic carbon dioxide (CO2) emissions. Emerging technologies such as the electrochemical synthesis of NH3 promise sustainable production from water, air, and renewable energies, but low TRLs are still reported. The electrification of the HB process opens a more viable path for sustainable NH3 production in the near future, where hydrogen (H2) is produced by electrolysis of water, powered from renewable energy sources. Many studies have focused on the production of 100 % green NH3 using only electric HB. In this work, a different approach is presented, which consists of studying the gradual incorporation of green H2 into a conventional NH3 plant. An Aspen Plus® V14 model of the methane-f... [more]

This work presents an improved thermodynamic model, an equilibrium model, and a unified kinetic model for ammonia synthesis. The thermodynamic model accurately describes the non-ideality of the reaction system up to 1000 bar using a modified Soave-Redlich-Kwong Equation-of-State. The developed Langmuir-Hinshelwood kinetic model accurately describes ammonia synthesis on iron-based catalysts by incorporating N* and H* surface species, whereas H* species are mainly relevant below 400°C. The model fits an extensive dataset across diverse conditions (251-550°C, 1-324 bar, H2/N2 ratios 0.33-8.5, and space velocities of 1-1800 Nm3 kg-cat-1 h-1) and accounts for catalyst activity variations through a Relative Catalytic Activity factor.

The United States’ Inflation Reduction Act (IRA) of 2022 has established incentives to facilitate the energy transition. While these policies provide economic incen-tives that encourage investment and may reduce financial risk for the private sector on the supply side, transitioning to a lower carbon or net-zero economy by 2050 presents several challenges. These include designing flexible production systems that can interact with inter-mittent renewable energy resources, ensure process safety, redesigning existing energy infrastructure to support new energy carriers like hydrogen or ammonia, and making long-term investment decisions in an uncertain and evolving market... (ABSTRACT ABBREVIATED)

Ammonia (NH3) has been receiving the attention of researchers as an alternative promising green fuel to replace fossil sources for energy production. However, the high NOx emissions are one of the drawbacks and restrictions of using NH3 on a broad scale. The current study investigates NO production/consumption for a 70/30 (vol%) NH3/H2 mixture using kinetic reaction mechanism concepts to shed light on the essential reaction routes that promote/inhibit NO formation. Sixty-seven kinetic reaction mechanisms from the literature have been investigated and compared with recently reported measurements at a wide range of equivalence ratios (ϕ) (0.6−1.4), atmospheric pressure and temperature conditions. Both numerical simulations and experimental measurements used the same combustion reactor configuration (premixed stabilized stagnation flame). To highlight the best kinetic model for the predicting of the NO experimental measurements of NO, a symmetric mean absolute percentage error (SMAPE) has... [more]

This study proposed two concepts for ammonia fuel storage for an ammonia-fueled ammonia carrier and evaluated these concepts in terms of economics. The first concept was to use ammonia in the cargo tank as fuel and the second concept was to install an additional independent fuel tank in the vessel. When more fuel tanks were installed, there was no cargo loss. However, there were extra costs for fuel tanks. The target ship was an 84,000 m3 ammonia carrier (very large gas carrier, VLGC). It traveled from Kuwait to South Korea. The capacity of fuel tanks was 4170 m3, which is the required amount for the round trip. This study conducted an economic evaluation to compare the two proposed concepts. Profits were estimated based on sales and life cycle cost (LCC). Results showed that sales were USD 1223 million for the first concept and USD 1287 million for the second concept. Profits for the first and second concepts were USD 684.3 million and USD 739.5 million, respectively. The second conce... [more]

This paper presents the results of a simulation study on the selection of an energy-optimal refrigeration system based on natural refrigerants as a function of outdoor climate parameters as a decision variable in a supermarket application. Simulations were conducted for twelve locations. Three new original refrigeration systems were presented: Cascade R744/R717 which is an advanced booster extended with an ammonia condensing system (CASC_1); Cascade R744/R717 with CO2 pump-fed MT and pressure-fed LT evaporators (CASC_2); and the R717 booster with CO2 pump-fed MT and LT evaporators (CB_NH3). As a reference system, a CO2 booster system with multi-ejectors and flooded evaporators (CB_EJ) was adopted. The CB_EJ system has been confirmed to be energy optimal for cold and temperate climates (Cfb, Dfa and cooler). In warm temperate climates (Csa, BSk, Cfa and similar), the energy consumption of CB_NH3 was the lowest. CASC_2 and CB_NH3 are energy optimal for hot climates (BWh, Af, Aw). The CB_... [more]

Arguably, one of the most important issues the world is facing currently is climate change. At the current rate of fossil fuel consumption, the world is heading towards extreme levels of global temperature rise if immediate actions are not taken. Transforming the current energy system from one largely based on fossil fuels to a carbon-neutral one requires unprecedented speed. Based on the current state of development, direct electrification of the future energy system alone is technically challenging and not enough, especially in hard-to-abate sectors like heavy industry, road trucking, international shipping, and aviation. This leaves a considerable demand for alternative carbon-neutral fuels such as green ammonia and hydrogen and renewable methanol. From this perspective, we discuss the overarching roles of each fuel in reaching net zero emission within the next three decades. The challenges and future directions associated with the fuels conclude the current perspective paper.

In this study, 3D premixed turbulent ammonia-hydrogen flames in air were studied using DNS. Mixtures with 75%, 50% and 25% ammonia (by mole fraction in the fuel mixture) and equivalence ratios of 0.8, 1.0 and 1.2 were studied. The studies were conducted in a decaying turbulence field with an initial Karlovitz number of 10. The flame structure and the influence of ammonia and the equivalence ratio were first studied. It was observed that the increase in equivalence ratio smoothened out the small scale wrinkles while leading to strongly curved leading edges. Increasing the amount of hydrogen in the fuel mixtures also led to increasingly distorted flames. These effects are attributed to local increases in the equivalence ratio due to the preferential diffusion effects of hydrogen. The effects of curvature on the flame chemistry were studied by looking at fuel consumption rates and key reactions. It was observed that the highly mobile H2 and H species were responsible for differential rate... [more]

Hydrogen is currently receiving significant attention and investment as a key enabler of defossilised global energy systems. Many believe this will eventually result in the international trade of hydrogen as a commodity from countries with significant renewable energy resources, for example New Zealand and Australia, to net energy importing countries including Japan and Korea. Japan has, since 2014, been actively exploring the components of the necessary supply chains, including the assessment of different hydrogen carriers. Public/private partnerships have invested in demonstration projects to assess the comparative merits of liquid hydrogen, ammonia, and organic carriers. On the supply side, significant projects have been proposed in Australia while the impending closure of New Zealand’s Tiwai Point aluminium smelter at the end of 2024 may provide an opportunity for green hydrogen production. However, it is also evident that the transition to a hydrogen economy will take some years a... [more]

The objective of this paper is to provide new data about the possibility of using ammonia as a carbon-free fuel in a spark-ignition engine. A current GDI PSA engine (Compression Ratio 10.5:1) was chosen in order to update the results available in the literature mainly obtained in the CFR engine. Particular attention was paid to determine the lowest possible load limit when the engine is supplied with pure ammonia or a small amount of H2, depending on engine speed, in order to highlight the limitation during cold start conditions. It can be concluded that this engine can run stably in most of these operating conditions with less than 10% H2 (of the total fuel volume) added to NH3. Measurements of exhaust pollutants, and in particular NOx, have made it possible to evaluate the possibility of diluting the intake gases and its limitation during combustion with pure H2 under slightly supercharged conditions. In conclusion, the 10% dilution limit allows a reduction of up to 40% in NOx while... [more]

Recently, ammonium carbamate (AC) has attracted attention as a substitute for urea, which is a commonly used reductant for NOx emitted from combustion engines. The AC exists as a solid at room temperature, and it is decomposed to NH3 and CO2 gases by heating. Therefore, adequate heat transfer is an essential issue in the design of AC pyrolysis reactor. In this study, a numerical model that describes the sublimation of AC was developed. For modeling, this study considered the three different calculation zones: solid-phase zone, gas-phase zone, and sublimation zone. Additionally, during the sublimation process, collapse of upper solid AC into the hollow space below by the effect of gravity is considered. As a result, it is presented that the modeling shows reasonable information about the AC sublimation in a reactor, such as temperatures in a reactor, pressure of reactor, and flow rate of sublimated gas. However, it is also found that accurate prediction of spatial temperature distributi... [more]

Global energy sources are being transformed from hydrocarbon-based energy sources to renewable and carbon-free energy sources such as wind, solar and hydrogen. The biggest challenge with hydrogen as a renewable energy carrier is the storage and delivery system’s complexity. Therefore, other media such as ammonia for indirect storage are now being considered. Research has shown that at reasonable pressures, ammonia is easily contained as a liquid. In this form, energy density is approximately half of that of gasoline and ten times more than batteries. Ammonia can provide effective storage of renewable energy through its existing storage and distribution network. In this article, we aimed to analyse the previous studies and the current research on the preparation of ammonia as a next-generation renewable energy carrier. The study focuses on technical advances emerging in ammonia synthesis technologies, such as photocatalysis, electrocatalysis and plasmacatalysis. Ammonia is now also stro... [more]

Gas-fired heat pumps are a potential replacement for condensing boilers, utilizing fossil-fuel resources more efficiently and reducing the amount of biogas or hydrogen required in sustainable gas grids. However, their adoption has been limited due to their large size and high capital cost, resulting in long payback times. For adsorption-based heat pumps, the major development challenge is to maximize the rate of heat transfer to the adsorbent, whilst minimizing the thermal mass. This work develops a modular finned-tube carbon−ammonia adsorption generator that incorporates the adsorbent in highly compacted 3-mm layers between aluminum fins. Manufacturing techniques that are amenable to low cost and high-volume production were developed. The module was tested using the large temperature jump (LTJ) method and achieved a time constant for adsorption and desorption of 50 s. The computational model predicted that if incorporated into two adsorption generators of 6 L volume each, they could b... [more]

In April 2018, the International Maritime Organisation adopted an ambitious plan to contribute to the global efforts to reduce the Greenhouse Gas emissions, as set by the Paris Agreement, by targeting a 50% reduction in shipping’s Green House Gas emissions by 2050, benchmarked to 2008 levels. To meet these challenging goals, the maritime industry must introduce environmentally friendly fuels with negligible, or low SOX, NOX and CO2 emissions. Ammonia use in maritime applications is considered promising, due to its high energy density, low flammability, easy storage and low production cost. Moreover, ammonia can be used as fuel in a variety of propulsors such as fuel cells and can be produced from renewable sources. As a result, ammonia can be used as a versatile marine fuel, exploiting the existing infrastructure, and having zero SOX and CO2 emissions. However, there are several challenges to overcome for ammonia to become a compelling fuel towards the decarbonisation of shipping. Such... [more]

Liquid ammonia is an ideal zero-carbon fuel for internal combustion engines. High-pressure injection is a key technology in organizing ammonia combustion. Characteristics of high-pressure liquid ammonia injection is lack of research. Spray behaviors are likely to change when a high-pressure diesel injector uses liquid ammonia as its fuel. This study uses high-speed imaging with a DBI method to investigate the liquid penetration, width, and spray tip velocity of high-pressure liquid ammonia injection up to 100 MPa. Non-flash and flash boiling conditions were included in the experimental conditions. Simulation was also used to evaluate the results. In non-flash boiling conditions, the Hiroyasu model provided better accuracy than the Siebers model. In flash boiling conditions, a phenomenon was found that liquid penetration and spray tip velocity were strongly suppressed in the initial stage of the injection process, this being the “spray resistance phenomenon”. The “spray resistance pheno... [more]

The European Union’s ambition to reach climate neutrality and a toxic-free environment by 2050 entails, among other things, cleaner road vehicles. The European Commission’s proposal for the next regulatory emissions standard, Euro 7, requires the measurement of pollutants currently not regulated on the road. In this study we compared a prototype portable emissions measurement system (PEMS) measuring CO2, CO, NO, NO2, N2O, NH3, CH4, and HCHO based on infrared laser absorption modulation (IRLAM), and two Fourier transform infrared (FTIR) spectrometers with laboratory grade analyzers. To this end, one Euro 6d Diesel, one Euro 6d gasoline, and one Euro 4 gasoline vehicle were tested at −7 °C and 23 °C with various driving cycles covering traffic conditions to highway dynamic driving. The results demonstrated that the differences among the instruments were small: ±1 mg/km for HCHO, N2O, and CH4, ±2.5 mg/km for NH3, ±10−15 mg/km for NOx, ±50 mg/km or ±15% for CO (whichever was larger), and ±... [more]

Carbon-free fuels, in particular ammonia and hydrogen, could play a significant role in the decarbonization of the mobility sector. In this work, the authors assessed the operation of a light-duty spark-ignition engine fueled with an ammonia−hydrogen blend (85% ammonia and 15% hydrogen by volume) using a 1D predictive model. Three-dimensional computations have been used in order to verify the reliability of the 1D model. The addition of hydrogen to the air−fuel mixture allows the operating capacity of the engine to be extended with respect to neat ammonia fueling. The engine can be properly regulated between 1500 rpm and 3000 rpm. Its operating range reduces as engine speed increases, and it cannot run at 6000 rpm. This is due to different engine operating constraints being exceeded. The maximum engine torque is about 240 Nm and is reached at 1500 rpm. The engine efficiency ranges between 42% and 19%, and the specific fuel consumption varies from about 350 g/kWh to about 750 g/kWh. The... [more]

Lean premixed combustion mode has become attractive for utilization in industrial gas turbines due to its ability to meet strict emissions regulations without compromising engine efficiency. In this combustion mode, the mixing process is the key player that affect the flame structure and stability, as well as the generated emissions. Many studies have investigated the aspects that influence premixed flames, including the effects of turbulence, combustor geometry, and level of partial premixing, while mostly using conventional natural gas fuel represented by methane. Recently, ammonia, a sustainable energy source, has been considered in gas turbines due to its carbon-free fuel producing no CO2. Utilizing 100% ammonia or a blend of methane and ammonia alters the combustion performance of a premixed flame due to the variation associated with the physical and chemical properties of ammonia. Thus, investigating the coupling between blend ratios and mixing length of methane-ammonia on flame... [more]

Ammonia is a toxic exhaust component emitted from internal combustion engines. Both pure ammonia and the products of its reaction with nitrogen and sulfur compounds, being the source of particulate matter (PM) emissions, are dangerous for human health and life. The aim of the article was to demonstrate that NH3 can be produced in exhaust gas after-treatment systems of spark-ignition (SI) engines used in light-duty vehicles. In some cases, NH3 occurs in high enough concentrations that can be harmful and dangerous. It would be reasonable to collect research data regarding this problem and consider the advisability of limiting these pollutant emissions in future regulations. The article presents the results of the spark-ignition engine testing on an engine test bench and discusses the impact of the air−fuel ratio regulation and some engine operating parameters on the concentration of NH3. It has been proven that in certain engine operating conditions and a combination of circumstances lik... [more]

This paper details the experimental and numerical analysis of a combustion process for atmospheric swirl burners using methane with added ammonia as fuel. The research was carried out for lean methane−air mixtures, which were doped with ammonia up to 5% and preheated up to 473 K. A flow with internal recirculation was induced by burners with different outflow angles from swirling blades, 30° and 50°, where tested equivalence ratio was 0.71. The NO and CO distribution profiles on specified axial positions of the combustor and the overall emission levels at the combustor outlet were measured and compared to a modelled outcome. The highest values of the NO emissions were collected for 5% NH3 and 50° (1950 ppmv), while a reduction to 1585 ppmv was observed at 30°. The doubling of the firing rates from 15 kW up to 30 kW did not have any great influence on the overall emissions. The emission trend lines were not proportional to the raising share of the ammonia in the fuel. 3D numerical tests... [more]

NO formation, which is one of the main disadvantages of ammonia combustion, was studied during the isochoric, adiabatic autoignition of ammonia/air mixtures using the algorithm of Computational Singular Perturbation (CSP). The chemical reactions supporting the action of the mode relating the most to NO were shown to be essentially the ones of the extended Zeldovich mechanism, thus indicating that NO formation is mainly thermal and not due to fuel-bound nitrogen. Because of this, addition of water vapor reduced NO formation, because of its action as a thermal buffer, but increased ignition delay, thus exacerbating the second important caveat of ammonia combustion, which is unrealistically long ignition delay. However, it was also shown that further addition of just 2% molar of H2O2 does not only reduce the ignition delay by a factor of 30, but also reverses the way water vapor affects ignition delay. Specifically, in the ternary mixture NH3/H2O/H2O2, addition of water vapor does not pro... [more]