When talking about the power generation either for electricity production or aviation propulsion, the main source of energy still comes from the combustion process. This comes from the energy released from chemical reactions, which involve oxidants and one or more fuels. Since the industrial revolution (1760) until now, many fuels have been employed to this end (wood, coal, oil, natural gas, etc.). Currently, the impact of GHG (greenhouse gases) regulations and the estimated depletion of fossil fuels
[9] are leading to a revolution in the combustion community, since new sustainable power fuels are required. In this context, new fuels, blends and new technologies are under investigation aiming at the reduction of the human carbon footprint.
2.1. Sustainable Biofuels
Further complexity introduced by zero-carbon fuels in terms of storage and emissions control, e.g., hydrogen and ammonia, opens up the possibility to use so-called sustainable fuels; in the aviation sector, these are known as sustainable aviation fuels (SAFs)
[10]. These fuels are similar to conventional fossil fuels, but they derive from sustainable feedstocks. In this way, the CO
2 abatement on the entire life cycle of the fuel would be 80%. They can be mixed with fossil fuels up to 50% without plants modifications, considerably reducing the GHG production.
As proposed by the International Civil Aviation Organization (ICAO), the most promising sustainable fuels are those based on the power-to-liquids (PtL) concept. Indeed, in the last H2020, the development of sun-to-liquid technologies has been funded by the European Union. These technologies are based on renewable energy, water, and CO2. In addition to this, researchers are exploring the production of synthetic jet fuel using green hydrogen (i.e., hydrogen generated by electrolysis). In particular, at Rotterdam’s Innovation Campus, highly innovative technologies are combined to produce jet fuel made (partly) from CO2 to achieve a carbon-neutral future for the aviation sector. The idea is to capture CO2 from the air and then to combine it with hydrogen produced by splitting water into hydrogen and oxygen with electrolysis. The result is a synthetic gas that can be transformed into a jet fuel. However, the project is still at the demonstration stage. Synthetic jet fuels still have a long way to go before they can become fully competitive, mainly due to their high costs.
Biofuels represent the kind of fuels coming from biomass such as plants and animal wastes, which has passed ups and downs from the second World War to the petroleum crisis in the 1970s. Currently, biofuels account for 3.4% of the total fuel employed in transportation, the most being produced in USA and Brazil
[5]. A brief classification can be made. The first generation of biofuels comes from human and animal feedstocks and are also called conventional biofuels. The second generation is based on no-food feedstocks and the third generation uses microalgae. Compared to biofuels, PtL technologies have the advantage to require less yields and water. On the contrary, even though the CO
2 production is balanced in the life cycle of the fuel, the emissions related to a hydrocarbon fuel remains (e.g., soot, NO
x, sulphur, etc.). Actually, it is worth underlining how energy-dense liquid fuels are the best suited in the aviation sector. For this reason, it is really important to research and develop new production methods that involve lower GHG emissions. In addition, it must be taken into account that producing and using SAFs will not totally solve the climate impact issue but will partially reduce it. This can be explained because of the emissions related to the SAF production methods and the water vapor emitted and the contrails formed during the flights (which are considered two of the most significant non-CO
2 climate-forcing impacts
[11]. These fuels, despite representing only 0.01% of the total fuel consumption, can represent a trustworthy and valuable solution during the transition to either zero carbon fuels or electric propulsion and mobility, but it does not represent a long-term solution for the GHG abatement.
2.2. Hydrogen
Currently, hydrogen is the main protagonist of the global energy future, being a carbon-free fuel. Indeed, many countries are working on programs at different levels (political, economic, technological) that endorse an even more carbon-neutral future. However, the hydrogen currently produced is not clean. Indeed, it is mainly produced using fossil fuels (96%); only the remaining 4% is produced by electrolysis. This means that more clean hydrogen needs to be produced. Indeed, different methods are employed to produce hydrogen: coal gasification with water vapor (brown H2), production from a generic fossil fuel (grey H2), or methane formation (steam methane reforming) together with the carbon capture and storage process (blue H2) and the electrolysis of water in special electrochemical cells powered by electricity produced from renewable sources (green H2). The latter is the cleanest way to produce hydrogen, and it can substitute the fossil fuels with the aim to make combustion systems more sustainable.
Hydrogen use in combustion is attractive because of its wide flammability range, large flame propagation speed, and small quenching distance. These properties can be observed in Table 1, which compares the main characteristic of H2 with conventional hydrocarbons used in aviation and industry (i.e., methane and kerosene). As summarized in Table 1, hydrogen shows wider flammability limits than those of conventional hydrocarbons. In details, the lean and rich flammability limits (LFL and RFL) in terms of volume % in air are equal to 4 and 75, respectively. Methane, on the other hand, is characterized by a flammability range of 5.5–15. Moreover, hydrogen has a higher flame propagation velocity than that of conventional fuels due to the faster reaction rates. Indeed, the flame speed in a stoichiometric H2/air mixture is 1.85 m/s with respect to the methane (0.44 m/s). Since no carbon is involved when pure H2 is burned, reactions including hydrocarbon intermediates, CO, and CO2, are eliminated. The primary pollutant species produced during hydrogen combustion are the nitrogen oxides (NOx).
Table 1. Comparison between properties of H2, CH4, and kerosene (T = 25 ∘C, p=1 atm and ϕ=1).
The use of blends of hydrogen and conventional hydrocarbons in gas turbines is one of the most promising technical solutions during the transition toward full decarbonization. Thanks to the H2 addition, the combustor can work in a leaner condition, thus with lower flame temperatures, which reduce NOx formation. In addition, the mixture enrichment with H2 involves the reduction of CO emissions. This is caused by two main factors: the reduction of carbon in the mixture due to the addition of H2 and the increased production of radicals that promotes the oxidation of CO to CO2.
Despite these positive aspects, hydrogen shows some other challenging technical issues that must be addressed, such as potential flashback and autoignition due to its significantly higher flame speed and shorter autoignition time. Furthermore, an excessive lean combustion can lead to dangerous thermoacoustic instabilities
[12,13,14,15,16,17][12][13][14][15][16][17]. This will require some modifications of current design features. Moreover, due to the low density of H
2, its volumetric energy density is less than half of that of other fuels. For example, in
Table 1, it can be seen that the lower heating value for H
2 is about 120 MJ/kg or 9.9 MJ/Nm
3. The corresponding value for CH
4 is 50 MJ/kg or 32.6 MJ/Nm
3 [18,19][18][19]. Thus, storing a sufficient amount of H
2 requires large volumes. A possible approach to this problem is storage at high pressures (68 MPa storage tanks are currently available and storage tanks up to 100 MPa will be available in the near future). Since the high complexity introduced by hydrogen, a great amount of research is necessary to fill the gap in terms of safety and storage. Meanwhile, many researchers suggest to store hydrogen in the form of ammonia, which is a fluid with physical properties close to the conventional gaseous fuels.
2.3. Ammonia
Green hydrogen has been recognized as a potential enabler of a carbon-free economy, but issues associated to its storage and distribution represent a barrier for its implementation. Hence, alternative media have been considered for indirect chemical storage. Among these media, ammonia has been identified as one of the most promising solution for both energy storage and direct combustion.
Ammonia is easy and cheap to store because it can be liquefied through compression at 8 bar (at room temperature), it is characterized by a high volumetric energy density (45% higher than liquid hydrogen), and it has a competitive gravimetric energy density (22.5 MJ/kg, making it comparable to low-ranked coals). It has been estimated that ammonia storage over 182 days costs 30 times less than hydrogen storage
[20]. Liquid ammonia contains 17.6% (in weight) of hydrogen, 1.7 times as much as liquid hydrogen itself (by volume)
[21]; thus, an ammonia tank (at 1 MPa) contains 2.5 times as much energy as a hydrogen tank (at 70 MPa)
[22], making ammonia a viable hydrogen-carrier fuel. Last, reliable infrastructures for production, transportation, and storage along with well-established safe handling procedures, already exist since ammonia has been massively produced throughout the world for more than a century, and it is one of the most transported bulk-manufactured chemicals in the world.
Ammonia is a colorless, light gas with a penetrating odor (density of 0.73 kg/m3, molecular weight of 17.03 kg/kmol). Under atmospheric condition, its boiling point is 239.8 K and its freezing point 195.5 K. Ammonia combustion is a topic of research because, being a carbon-free molecule, its products are only molecular nitrogen gas and water. Nevertheless, ammonia combustion is challenging due to its thermokinetic properties: high autoignition temperature (930 K compared to 859 K of methane), low laminar flame speed (about 5 times lower than that of methane), low flammability limits (18% to 28% by volume in air at atmospheric pressure), and lower heating value (18.6 MJ/kg) which make pure ammonia combustion difficult. Another issue associated to ammonia combustion is its propensity to emit large amounts of NO when burned. Contrary to conventional fuels, here, most of the NO is formed via fuel NOx pathways. Hence, reducing flame temperature by operating lean, to penalize thermal NOx pathways, is ineffective with ammonia-air flames to abate NO emissions below acceptable limits. For these reasons, blends with more reactive fuels such as methane and hydrogen have been attempted for practical applications.
In particular, ammonia-methane blends have been identified as a relatively easy technology to implement for a cofiring application, since the two fuels share similar density, viscosity, and heat capacity. Stability limits and exhaust NO performances of ammonia–methane–air swirled flames in a laboratory-scale burner has been experimentally determined over a wide range of equivalence ratios, ammonia fuel fractions, and operating pressures (up to 5 bar)
[23] (This article was published in Experimental Thermal and Fluid Science, 114, A.A. Khateeb, T.F. Guiberti, X. Zhu, M. Younes, A. Jamal, W.L. Roberts, Stability limits and exhaust NO performances of ammonia-methane-air swirl flames, 110058, Copyright Elsevier (2020)). Results show that the stability region for ammonia–methane mixtures is given by three different limits: the lean blowout limit, the flashback limit, and the additional rich blowout limit (see
Figure 1). For ammonia fuel fractions less than 50%, the stability region is bounded by lean blowout and flashback limits. The increase in the ammonia fuel fraction enlarges the flashback limit due to the reduced reactivity of the mixture, but it also increases the lean blowout limit. The equivalence ratio at flashback increases regularly with ammonia addition up to
χNH3=0.50, where a transition happens: here, even for equivalence ratio greater than unity, the flame is not fast enough to flashback. Thus, for higher ammonia fuel fractions, the flame extinction is due only to rich or lean blowout and the stability region enlarges.
Figure 1. Stability limits of ammonia–methane–air swirl flames as a function of the ammonia fuel fraction (geometric swirl number
Sg=1.00 and
Re=5000), (adapted with permission from
[23]. 2020, Elsevier).
Measurements of NO concentration in the exhausts show that reasonably low NO concentrations (<100 ppm) can only be found for stoichiometric or rich equivalence ratios. Under these conditions, for a fixed equivalence ratio, ammonia addition lowers NO concentrations. Under lean conditions, NO emissions exceed the limits imposed by current regulations by at least one order of magnitude (see Figure 2). As already mentioned, this is due to the fuel pathways of formation of NO different from thermal pathways. From a technological standpoint, this means that burners operating in lean premixed conditions with ammonia–methane flame that satisfy current regulations on NO emissions are far from feasible and that a two-stage combustion process is required to ensure globally lean operation and to avoid harmful unburned NH3 emissions. Moreover, the blending of methane and ammonia can lead to the formation of hydrogen cyanide (HCN), which is a key point to be investigated.
Figure 2. Measured exhaust NO concentration in parts per million (ppm) as a function of equivalence ratio (adapted with permission from
[23]. 2020, Elsevier).
The issue related to the low reactivity of ammonia can be mitigated by blending with a more reactive fuel such as hydrogen. Recent studies
[24,25][24][25] showed that ammonia–hydrogen flames can be stabilized and that broader stable range compared to pure hydrogen or ammonia can be achieved. Furthermore, due to the high reactivity of hydrogen, ammonia–hydrogen–air combustion can be operated at lean conditions with competitive NO emissions (few hundreds of ppm or less). For these reasons, lean ammonia–hydrogen–air blends are promising candidates for gas turbines since elevated pressure is expected to reduce NO emissions even further. The main limitation of lean ammonia–hydrogen–air flames is the elevated production of N
2O under certain operating conditions
[26]. N
2O is a dangerous greenhouse gas, around 250 times more effective than CO
2, and thus, it could potentially cancel the benefits associated with a carbon-free combustion. It is clear that some trade-off between NO and N
2O emissions exist and this topic is receiving a great amount of attention. Recently, stability limits and exhaust NO emissions of premixed ammonia–hydrogen–air swirled flames were measured in a laboratory-scale burner for a wide range of pressure, up to 5 bar
[27]. The full range of ammonia fractions in the fuel was investigated. Stability limits were found to have a similar trend to methane–ammonia flames, but equivalence ratios at lean blowout and flashback are smaller for ammonia–hydrogen flames, resulting in a narrower zone of stability for lean conditions. Furthermore, the critical ammonia fuel fraction for which transition from flashback to rich blowout happens is larger for ammonia–hydrogen blends. It must be noted that for hydrogen fraction above 10 %, flames can be stabilized for equivalence ratio even smaller than
ϕ=0.6 in this burner. This lean condition is competitive in terms of NO emissions (between 100 and 160 ppm). Unfortunately, N
2O emissions may become unacceptably large if the flame is operated with a low equivalence ratio.
As already stated, ammonia could be used as an hydrogen carrier, exploiting its vast infrastructure system to transport hydrogen from the production plant to the location of use. Here, ammonia must be partially dissociated (the process is also referred as cracking) resulting in a blend including nitrogen in addition to hydrogen, with a 3:1 nitrogen to hydrogen volume ratio. The stability limits of this blend show similar trends of ammonia–hydrogen blends
[25].
Ammonia has been identified as a sustainable fuel for gas turbines and a potential enabler of the hydrogen economy. Research about the use of ammonia for large power generation is still ongoing—in particular, on the ill-defined kinetic processes that occur at high power outputs using various blends of ammonia with gases such as methane and hydrogen. Use of ammonia in propulsion system is receiving increasing interest. The potential of methane–ammonia–oxygen blends to allow deflagration to detonation transition and its applicability in propulsion system, has been discussed
[28,29][28][29]. Results showed that flame speeds were modest for all mixtures where the oxygen percentage was 39% or less. Microthrusters for propulsion of small space vehicles, fueled with ammonia and acetylene have been studied and developed in Russia, China, and USA
[30,31][30][31]. Although the technology is promising, literature on micropropulsion systems using ammonia as a fuel is still scarce, opening the possibilities for further research.