energies

Review
Hydrogen Combustion: Features and Barriers to Its Exploitation
in the Energy Transition
Eugenio Giacomazzi *,†,‡ , Guido Troiani ‡ , Antonio Di Nardo ‡ , Giorgio Calchetti ‡ , Donato Cecere ‡ ,
Giuseppe Messina ‡ and Simone Carpenella ‡

Laboratory of Processes & Systems Engineering for Energy Decarbonisation, ENEA, via Anguillarese 301,
00123 Rome, Italy; [Link]@[Link] (G.T.); [Link]@[Link] (A.D.N.); [Link]@[Link] (G.C.);
[Link]@[Link] (D.C.); [Link]@[Link] (G.M.); [Link]@[Link] (S.C.)
* Correspondence: [Link]@[Link]
† Current address: Casaccia Research Center, TERIN-PSU-IPSE, S.P. 081, ENEA, Via Anguillarese 301,

S.M. Galeria, 00123 Rome, Italy.

‡ These authors contributed equally to this work.

Abstract: The aim of this article is to review hydrogen combustion applications within the energy
transition framework. Hydrogen blends are also included, from the well-known hydrogen enriched
natural gas (HENG) to the hydrogen and ammonia blends whose chemical kinetics is still not clearly
defined. Hydrogen and hydrogen blends combustion characteristics will be firstly summarized in
terms of standard properties like the laminar flame speed and the adiabatic flame temperature, but
also evidencing the critical role of hydrogen preferential diffusion in burning rate enhancement and
the drastic reduction in radiative emission with respect to natural gas flames. Then, combustion
applications in both thermo-electric power generation (based on internal combustion engines, i.e.,
gas turbines and piston engines) and hard-to-abate industry (requiring high-temperature kilns and
furnaces) sectors will be considered, highlighting the main issues due to hydrogen addition related to
safety, pollutant emissions, and potentially negative effects on industrial products (e.g., glass, cement
and ceramic).

Citation: Giacomazzi, E.; Troiani, G.;

Keywords: hydrogen combustion; hydrogen blends; power generation; gas turbines; hard-to-abate
Di Nardo, A.; Calchetti, G.; Cecere,
industry
D.; Messina, G.; Carpenella, S.
Hydrogen Combustion: Features and
Barriers to Its Exploitation in the
Energy Transition. Energies 2023, 16,
7174. [Link]
1. Introduction
en16207174 According to the International Energy Agency, energy efficiency, behavioral change,
electrification, renewables, hydrogen and hydrogen-based fuels, and carbon capture, utiliza-
Academic Editors: Samuel Simon
Araya and Liso Vincenzo
tion, and storage (CCUS) are the key pillars to decarbonizing the global energy system [1].
The increasing share in cumulative emission reductions due to hydrogen justifies its im-
Received: 25 September 2023 portant role in the net zero emissions scenario [1] to decarbonize sectors where emissions
Revised: 16 October 2023 are hard to abate, such as heavy industry and long-distance transport. Within the power
Accepted: 19 October 2023 sector, hydrogen holds the potential to deliver flexibility by aiding in the management of
Published: 20 October 2023 increasing proportions of fluctuating renewable energy generation. Additionally, it can play
a role in enabling seasonal energy storage, further enhancing the versatility and reliability
of the energy system.
Copyright: © 2023 by the authors.
Hydrogen stands out as an exceptionally versatile fuel that can be generated using a
Licensee MDPI, Basel, Switzerland. wide spectrum of energy sources, encompassing coal, oil, natural gas, biomass, renewables,
This article is an open access article and nuclear power. The production methods are equally diverse, spanning processes like
distributed under the terms and reforming, gasification, electrolysis, pyrolysis, water splitting, and numerous others. In
conditions of the Creative Commons recent times, distinct colors have been assigned to signify different pathways of hydrogen
Attribution (CC BY) license (https:// production: “green” for hydrogen extracted through electrolysis with electricity from
[Link]/licenses/by/ renewable sources; “grey” for H2 produced from fossil raw materials such as natural
4.0/). gas (this generates around 10 tons of CO2 per ton of H2 ); “blue” for production derived

Energies 2023, 16, 7174. [Link] [Link]

Energies 2023, 16, 7174 2 of 29

from fossil fuels with CCUS; “turquoise” for H2 produced by splitting natural gas at
high temperatures (only solid carbon is produced in the process, i.e., no CO2 is emitted
if the process runs on heat from renewable energy sources). Due to the multitude of
energy sources that can be employed, the environmental consequences associated with
each method of hydrogen production can differ significantly. Moreover, the geographic
location and the specific configuration of the process also play a crucial role in shaping
these environmental impacts.
As of 2020, the worldwide demand for hydrogen amounted to approximately 90 mil-
lion metric tons (Mt) [1], indicating a growth of 50% since the year 2000. Nearly the entirety
of this demand is attributed to applications in refining and industrial sectors. Refineries, on
an annual basis, utilize nearly 40 million metric tons of hydrogen for tasks such as feedstock
and reagents, as well as an energy source.
Demand is slightly elevated in the industrial sector, surpassing 50 million metric
tons (Mt) of hydrogen [1]. This demand is primarily attributed to its use as feedstock.
Within the chemical production sector, approximately 45 million metric tons of hydrogen
are consumed, with roughly three-quarters allocated to ammonia production and the
remaining one-quarter directed towards methanol production. The remaining 5 million
metric tons of hydrogen find usage in the direct reduced iron (DRI) process for steelmaking.
This allocation of demand has remained nearly unchanged since 2000, with only a marginal
uptick in demand noted for DRI production.
Simultaneously, mounting concerns about climate change have led to heightened
awareness, prompting both governments and industries to make resolute pledges aimed
at curtailing emissions. While this has expedited the integration of hydrogen into novel
applications, the demand in this realm still remains quite limited. For instance, in the
transport sector, the yearly hydrogen demand stands at less than 20 thousand metric tons
(kt) of hydrogen, representing a mere 0.02% of the overall hydrogen demand. As illustrated
in the IEA roadmap for achieving a net-zero state by 2050 [2], achieving government
decarbonization objectives will necessitate a significant and abrupt acceleration in the
adoption of hydrogen technologies across various segments within the energy sector.
In the net zero emissions scenario [2], the demand for hydrogen experiences a sub-
stantial increase, expanding nearly six times its current value to reach 530 million metric
tons (Mt) of hydrogen by the year 2050. This surge in demand is divided, with half of
it being allocated to the industry and transport sectors. In this scenario, the presence of
hydrogen in the power sector undergoes a marked increase. Its utilization in gas-fired
power plants and stationary fuel cells plays a crucial role in mitigating the challenges
associated with the growing output from variable renewable sources, facilitating the inte-
gration of larger proportions of solar photovoltaic (PV) and wind energy, and furnishing
seasonal energy storage solutions. Additionally, hydrogen’s application in buildings also
encounters growth, although its adoption remains constrained to specific circumstances. In
the same scenario projected for 2050, approximately one-third of the hydrogen demand
is allocated to the production of hydrogen-based fuels. These fuels include ammonia,
synthetic kerosene, and synthetic methane. Current applications of ammonia are primarily
centered around nitrogen fertilizers, but now the interest is growing in other sectors, such
as the long-distance shipping of hydrogen and combustion, where the co-firing of ammonia
in coal-fired power plants has shown successful demonstrations; however, further research,
development, and deployment efforts are necessary to advance the utilization of pure
ammonia as a direct fuel source (also thermally and catalytically decomposed) in steam or
gas turbines [3].
When hydrogen is burned, the primary resultant is water (H2 O), rendering it a gen-
uinely emission-free fuel in terms of CO2 . The ultimate objective is to utilize 100% green
hydrogen for combustion, entirely supplanting natural gas. In the interim, a more immedi-
ate goal involves blending hydrogen with natural gas to be used in gas turbines and other
industrial combustion applications, thereby achieving a partial reduction in CO2 emissions.
Nowadays, the term fuel-flexibility refers to combustion-based power generation system
Energies 2023, 16, 7174 3 of 29

(especially gas turbines) capabilities to operate with hydrogen blends as fuel in a stable,
safe, and reliable way when the H2 content unpredictably varies in time due to intermit-
tent production from renewables. Such blends range from hydrogen-enriched natural gas
(HENG) to ammonia (a promising H2 -carrier).
An important but frequently overlooked factor that is easily comprehensible is the
necessity for a substantial proportion of hydrogen by mass in fuel mixtures to produce a
noteworthy impact on CO2 emissions. It is common to discuss these proportions in terms of
volume fractions, but in the context of methane/hydrogen blends, the volume percentage
of H2 significantly differs from its mass equivalent, as illustrated in Figure 1. For instance,
30% and 50% volume correspond to just 5% and 11% mass, while achieving an emission
reduction of 55% necessitates an 80% volume fraction. Nevertheless, even maintaining a
low 30% volume fraction becomes quite challenging when factoring in significant temporal
fluctuations in composition.

Figure 1. Correlation between volume and mass percentages within methane/hydrogen blends, and
its consequential effect on CO2 emissions (considering an assumed electrical efficiency of 55% in the
computation). The percentage values on the left are in reference to pure methane.

Adopting hydrogen in combustion application is not straightforward. A fuel consist-

ing in 100% hydrogen necessitates an extra volumetric flow of 208%, approximately three
times more than that needed for methane to have the same power; hence, depending on
the blend percentage, there might be a need to expand the size of piping and valves to
manage the higher volumetric flow demanded by hydrogen. Its physical characteristics
introduce complexities in terms of production, storage, and transportation, setting it apart
from natural gas. Safety issues also arise due to hydrogen’s broader flammability range,
lower vapor density, and faster flame speed, necessitating careful consideration within the
framework of system design. Safety mechanisms for gas detection and fire protection must
be adjusted to address hydrogen’s unique volatility and distinctive detection characteristics.
Correspondingly, measures for explosion-proofing should be equipped to confine more
substantial explosions, and modifications to ventilation systems are essential. Moreover,
hydrogen encounters distinctive challenges related to supply and infrastructure. The fuel
system’s pipelines and valves enclosed must harmonize with hydrogen, necessitating mate-
Energies 2023, 16, 7174 4 of 29

rials that are hydrogen-compatible and designed with safety factors in mind. Additionally,
the design must incorporate hydrogen-tight seals capable of accommodating the small
hydrogen gas molecules.
In this article, the combustion features of hydrogen enrichment in fuel blends will be
firstly considered, also briefly looking at the effects on materials. Then, an overview of
combustion applications in power generation and hard-to-abate sectors will be provided to
identify the state-of-the-art and the barriers for its exploitation. In the end, conclusions and
future directions will be drawn.

2. Features of Hydrogen Combustion

When employing hydrogen either alongside natural gas or as a complete substitute, it
is crucial to grasp the distinctions between these two fuels.
Hydrogen possesses a density that is one-ninth that of natural gas, and it holds the
distinction of being the smallest known molecule. This characteristic introduces challenges
regarding transportation and sealing. Furthermore, hydrogen’s heating value is merely
one-third that of natural gas (on a volumetric basis), signifying that three times the amount
of hydrogen fuel is necessary to generate an equivalent power output compared to nat-
ural gas. In hydrogen combustion, although a higher volume flow of fuel is needed for
equivalent energy production, about 20% less air by volume is necessary to generate a
flame comparable to natural gas. This reduction in the air volume requirement results
in a decreased mass flow through the combustor, subsequently reducing convective heat
transfer. From this standpoint, flue gas recirculation can be employed to increase the mass
flow of air into the combustor, thereby increasing convective heat transfer and lowering the
flame temperature, as discussed in [4–6].
Moreover, hydrogen has a considerably broader flammability range than natural
gas, leading to heightened concerns regarding environmental, health, and safety aspects
during both hydrogen transportation and combustion. Although it has recently been ob-
served [7] that mixtures containing higher H2 concentrations are slower to ignite compared
to those with higher CH4 concentrations at low temperatures (below 930 K, for hydrogen
combustion, the self-recombination of HO2 radicals leads to chain propagation which
inhibits reactivity, whereas for methane combustion, the reaction between radicals and
HO2 leads to chain branching, increasing reactivity), for higher temperatures hydrogen
largely enhances the reactivity of fuel blends: the ignition delay time decreases [8–11];
at room temperature and pressure, the flammability limits (0.1–7.1) are well wider than
those of natural gas (0.5–1.67); the flame speed is higher [12] and the critical strain rate
increases, thus reducing potential flame quenching [13,14]. At a fixed equivalence ratio
(Φ), the hydrogen/air premixed flame burns with an adiabatic flame temperature higher
than the corresponding natural gas one (see Figure 2, left). In the same way, fixing the
equivalence ratio, the increase in the hydrogen content in a methane/hydrogen mixture
can rise the adiabatic flame temperature (see Figure 2, right).
Figure 3 reports data on laminar and turbulent flame speed from [15,16] for CH4 /H2
fuel mixtures with hydrogen content up to 50% vol. The data are specific to lean premixed
fuel/air mixtures (0.4 < φ < 0.5) at 5 bar, preheated at 673 K, flowing at 40 m/s, and with
a 15% inlet turbulence intensity. Laminar flame speed values were calculated based on
the GRI3.0 chemical mechanism. The data on turbulent flame speed show the unexpected
effects of increasing the hydrogen content. Initially, there is a moderate, nearly linear
increase in turbulent flame speed, following the trend of calculated laminar flame speed,
but the linearity varies with the equivalence ratio, is longer for leaner mixtures. This
suggests complex interactions between hydrogen addition and combustion properties. The
differences (evident in the richer mixtures in Figure 3) highlight the presence of both the
chemical kinetics and physical (diffusivity, thermal conductivity, turbulence) effects of the
hydrogen addition: the linear trends depict the chemical kinetics reaction properties of
the fuel gas mixtures; beyond the limits of the linear region, the turbulent flame speed
rapidly diverges (similar trends are observed for the leaner conditions but shifted towards
Energies 2023, 16, 7174 5 of 29

higher hydrogen concentrations). Hence, besides the chemical kinetics effects influenced by
hydrogen, which are reflected in changes in the laminar flame speed, the physical properties
of hydrogen also accelerate the consumption rate of the fuel species. One of the physical
effects is that the presence of hydrogen in air/hydrocarbon blends, especially at the leaner
equivalence ratios, decreases the Markstein length, even to negative values [17,18]. Thus, a
positively stretched flame increases its laminar combustion velocity, in contrast to a pure
hydrocarbon/air flame (with a positive Markstein number along its whole flammability
limit), whose laminar combustion velocity is increased when negatively stretched. The
increase in hydrogen content is shown to lower the thickness of the flame pre-heat zone,
while the heat release zone seems to be insensitive to turbulence effects, at least in the
broadened preheat-thin reaction zone [19]. Some other physical effects of the hydrogen
addition will be discussed in Section 2.1.

Figure 2. Adiabatic flame temperature vs. equivalence ratio (Φ) for hydrogen and methane flames in
air (left), and vs. hydrogen content for some specific mixtures (right) [15].

Figure 3. Laminar and turbulent flame speed for CH4 /H2 fuel mixtures with different hydrogen
from [15]. Laminar flame speed data come from chemical kinetics calculations based on the GRI3.0
chemical mechanism. Turbulent flame speeds come from experimental measurements.

The higher hydrogen combustion temperatures produce an increase in nitrogen oxides,

NOx , most of which is thermal, i.e., coming from high-temperature regions with sufficiently
long residence times [20]. This is one of the main concerns in operating burners with fuel
Energies 2023, 16, 7174 6 of 29

blends having a high H2 content. Also, turbulence plays its role in the formation of NOx ,
e.g., they are reduced as the Karlovitz number and the H2 content are increased, and the
turbulent flame brush thickened [21].
Being a fundamental aspect in any combustion process, chemical kinetics is now
embraced as a closing topic in this introduction on hydrogen characteristics. Detailed
chemical kinetics mechanisms are effective in computing the key properties of simplified
flames, including adiabatic flame temperature, flame speed, and autoignition delay time.
Moreover, they find use in fluid dynamics calculations that aim to simulate actual combus-
tion systems. Since such simulations become excessively demanding when coupled with
detailed chemistry and the transport of each individual species involved in the chemical
mechanism adopted, real-world combustion systems can be represented through a network
of simplified chemical reactors, where very detailed chemistry can be applied [22].
Hydrogen reactions play a central role in the combustion kinetics of any fuel. Specif-
ically in the context of hydrogen combustion, the Konnov mechanism [23,24] has been
recently developed, also in conjunction with carbon chemistry. These mechanisms are
highly detailed and exhibit good agreement with experimental data, as well as with other
significant kinetic models. In [23], a comparison was made between experimental and
computational results employing two modern and comprehensive chemical kinetic mecha-
nisms, Glarborg [25] and POLIMI [26]. Discrepancies were observed, particularly at rich
equivalence ratios, but the Konnov model [23] demonstrated a strong overall performance
in replicating laminar burning velocities and NO concentrations. At lean equivalence ratios,
the adiabatic burning velocities from both numerical and experimental studies matched
quite closely, with minor distinctions emerging under rich conditions, where the Konnov
model aligned more closely with experimental values despite inherent uncertainties. In the
prediction of NO levels, the Konnov model also came closest to experimental outcomes, dis-
playing only slight deviations, primarily under rich conditions where other kinetic schemes
underperformed. This superior performance in rich conditions was attributed to the Kon-
nov model’s better approximation of prompt, or Fenimore, NOx formation. Nonetheless, it
is worth noting that the Konnov mechanism is not the sole kinetic mechanism under con-
sideration for hydrogen-containing fuels. The AramcoMech 1.3 mechanism [27] has been
effectively used to predict autoignition delay times for hydrogen-containing mixtures [10].
Despite advancements in the development of chemical kinetic schemes, uncertainty persists
regarding the optimal approach to describe the full spectrum of properties across various
natural gas blends with hydrogen.

2.1. Effects on Flame Stability

Combustion in excess of air can mitigate NOx production [28], but at these conditions
of extremely lean combustion, the gaseous mixtures rich in hydrogen are characterized by
a disparity between the diffusion by mass and the thermal one, inducing phenomena of
intrinsic instability with a strong impact on the laminar and turbulent combustion speed,
and thus altering the flame topology.
These effects have been theoretically predicted [29–31], as well as experimentally [32,
33] and numerically visualized (numerical simulations) [34–36]. In particular, these reactive
mixtures are extremely sensitive to some external perturbations (usually present in every
burner) producing exponential growths in the extension of the flame front, in pressure
fluctuations, as well as in temperature, with a negative impact on the performance of
thermal machines, their polluting emissions, and even their life time. However, with an
accurate design of the combustion chamber, it is possible to maximize the advantages
deriving from these instabilities, i.e., the increase in the average combustion speed (and
therefore, in the thermal power) and compactness of flames (smaller size of the devices),
while eliminating or mitigating the negative aspects, such as high pressure and temperature
fluctuations, localized quenching and flashbacks.
Hydrogen, and light species in general, diffuse preferentially with respect to other
species in a mixture. In recent decades, so-called asymptotic theories [29–31] have been
Energies 2023, 16, 7174 7 of 29

developed which predict the existence of perturbations (in specific wavelength ranges)
that are particularly effective in destabilizing combustion processes, which strongly de-
pend on the Lewis number of the mixture. The Lewis number (Le) represents a measure
of the disparity between thermal and mass diffusivity, through their ratio: therefore, a
hydrogen-rich mixture, which has a mass diffusivity that is extremely greater than the
methane molecule, will be characterized by a Lewis number less than unity. In a premixed
combustion, this makes the local equivalence ratio lower or higher than the inlet nominal
equivalence ratio of the considered fuel blend depending on the local flame curvature. An
example is provided in Figure 4 for a CH4 /H2 —air flame at a nominal Φ = 0.7 and 20%
H2 volume content [37], where the instantaneous flame surface (identified by means of the
progress variable value related to the maximum heat release) is shown, evidencing local
hydrogen enrichment in positive curvature regions, and a decrease in the equivalence ratio
in negative curvature regions. This mechanism changes flame speed locally, and tends to
enhance the wrinkling of the flame front and the burning rate.

Figure 4. Snapshot of a progress variable iso-surface associated to the maximum heat release colored
with its normalized curvature and two iso-surfaces of equivalence ratio at Φ = 0.657 (blue) and
Φ = 0.757 (orange), respectively, for a CH4 /H2 —air flame at a nominal Φ = 0.7 and X H2 = 0.2 [37].

Mixtures with Lewis numbers smaller than a critical value (Lec , generally less than one)
will be characterized by small-scale (thermo-diffusive) and large-scale (hydro-dynamic)
instabilities. With a Lewis number close to the Lec or greater, mainly hydro-dynamic
instabilities will survive. This type of instability is based on different formation mechanisms.
In the case of thermo-diffusive instabilities, the high diffusivity of the mixture (in particular
of H2 ) will give rise, when the flame front is perturbed/corrugated, to inhomogeneity of the
equivalence ratio of the mixture and of the local temperatures with a consequent variation
of the local laminar combustion speeds, which in turn will amplify the initial perturbations
of the front, making it even more corrugated. Such corrugations increase the turbulent
flame speed, as shown in Figure 5, that reports the ratio between the turbulent and laminar
flame speeds of a premixed CH4 /H2 /Air Bunsen flame: the lower the Lewis number and
the higher the turbulence intensity, the higher the turbulent flame speed will be [38,39].
This phenomenon is more effective with more perturbations, and the corrugations of
the front are small in scale. In the case of Le > Lec , this phenomenon is strongly limited,
and what arises is a hydro-dynamic type mechanism, in which the large-scale corrugations
Energies 2023, 16, 7174 8 of 29

of the front compress or expand the stream lines of the flow field, thus channeling areas
with low or high velocity upstream of the flame front. Also, this mechanism initially tends
to amplify small-amplitude perturbations.

Figure 5. Ratio between turbulent and laminar flame speeds versus the effective Lewis number, as
defined in [40], in a premixed CH4 /H2 /Air Bunsen flame, parameterized with turbulence intensity
of the jet, from studies in [38,39].

The presence of thermo-diffusive instabilities alone is not possible. In fact, since the a
phenomenon of hydro-dynamic instability is always present in a flame, due to the difference
in temperature between reactants and combustion products, that of the thermo-diffusive
type is driven by the disparity between the mass and thermal diffusivity, which can be
eliminated by acting on the composition of the reactant mixture. Studies present in the
literature have shown the interaction, in Bunsen geometries, of hydrodynamic instabilities
with flow turbulence [41–45], while the characterization of the interaction of turbulence
with both instabilities (hydro-dynamic and thermo-diffusive) still lacks.
Due to its elevated combustion temperature and faster flame speed, hydrogen combus-
tion presents an increased susceptibility to instability, potentially leading to flameouts and
flashback incidents. Specifically, the heightened reactivity of hydrogen inherently raises
the risk of self-ignition and flashbacks, primarily within the premix section. This concern
becomes even more critical in systems characterized by exceedingly high inlet air temper-
atures, such as those found in highly recuperated gas turbines, as referenced in [46,47].
Furthermore, hydrogen flames exhibit a substantially different thermoacoustic behavior
compared to natural gas flames, owing to their higher flame velocity, shorter ignition delay,
and distinct flame stabilization mechanisms. These differences result in varying flame
shapes, positions, and reactivity. Consequently, the potential for combustion dynamics,
characterized by self-sustained oscillations at the acoustic frequency of the combustion
chamber, is higher in gas turbines running on hydrogen-enriched fuels than in natural gas
operation, as indicated in [48,49]. This implies that undesired and hazardous phenomena,
such as combustion instability, flashbacks, and lean-blowouts, can manifest not only during
steady-state operation but also during transient regimes. For instance, these issues may
arise when the power output changes rapidly or when the fuel composition undergoes
variations.

2.2. Effects on Pollutant Emissions

The main emission indicators on which the performance of burners are based are
mainly the nitrogen oxides NOx , composed of NO and NO2 , CO and carbon dioxide CO2 .
There is no fundamental chemical kinetic reason why H2 flames should produce more
NOx than natural gas flames. Since most NOx is thermal, i.e., produced where reactants
are at a high temperature for a sufficiently long residence time (above a certain threshold
Energies 2023, 16, 7174 9 of 29

temperature, around 1800 K, the production of NOx increases dramatically), more lean
mixtures have to be adopted to reduce the peak temperatures (see Figure 2) when burning
fuel blends with higher a H2 content.
Figure 6 (top) shows a map of NOx emissions as a function of the equivalence ratio
and hydrogen content for a CH4 /H2 blend reacting with air at two different pressures [50]:
respecting NOx emission limits requires that one operates at an equivalence ratio well below
0.5, especially at high H2 content and high pressure. The implementation of exhaust gas
recirculation (EGR) can be of help in reducing NOx emissions in different applications (see
Figure 6, bottom), and in gas turbines, it is a potential solution to enhance their turn-down
ratio, i.e., to reduce their partial load (minimum technical environmental load).

Figure 6. NOx emissions in ppm vs. equivalence ratio and hydrogen content for a CH4 /H2 blend
reacting with air without and with dilution through exhaust gas recirculation (EGR). Two pressures
are considered: 1 bar (left) and 25 bar (right). The initial temperature of reactants changes with the
hydrogen content: without EGR, it is in the range of 750–820 K, and with EGR, it is in the range of
800–850 K, decreasing while H2 is increased [50].
Energies 2023, 16, 7174 10 of 29

Apart from NOx predictions and expectations from chemical kinetics calculations,
some direct measurements of NOx emissions in a specific premixed Bunsen burner at
1 atmosphere are here reported due to the interesting operational strategy implemented
to avoid flashback occurrence [39]: as the hydrogen content increases in the CH4 /H2 fuel
blend, driving the increase in flame propagation speed, the value of the equivalence ratio
is decreased by increasing the excess air. This strategy allowed to maintain the flame
propagation speed constant (0.33 m/s), and at the same time, lowered the adiabatic flame
temperature; additionally, the power was kept constant (7.1 kW) by raising the flow rate of
the reactant mixture. Such a strategy avoided a flashback up to the maximum jet Reynolds
number (explored range, 10.000–13.900) in [39]: it would be interesting to see what happens
at higher turbulent jet Reynolds numbers to check the effects on the nonlinear increase in
the turbulent flame speed. The measurements of emissions were carried out at the chimney,
taking a small quantity of combustion products and analyzing them by means of the FTIR
(Fourier transform infrared spectroscopy) technique [51,52].
Figure 7 shows the quantity of NOx expressed in parts per million (ppm), scaled to
a value of oxygen in the combustion equal to 15%, as well as in mass normalized by the
fuel energy actually converted into heat, to take into account the different composition of
exhausts while increasing the hydrogen content [39]. Additionally, in this way, the emission
values of machines of significantly different sizes (power) can be compared. It is observed
that, above a hydrogen mole fraction of 45–50%, emissions decrease dramatically. This is
due to the regulation strategy adopted in [39]: while the hydrogen content is increased,
the equivalence ratio is decreased, thus lowering the flame temperature and thermal NOx
contribution (the most relevant). In fact, the temperature changes from about 2100 K for
the methane flame to nearly 1600 K for the hydrogen one.

Figure 7. NOx concentration in ppm (blue squared symbols) and mg/MJ (red diamonds) as the
hydrogen content (expressed in molar fraction, X) varies in the premixed CH4 /H2 /Air Bunsen
flames studied in [39]. Values are scaled at an oxygen content of 15%.

Figure 8 shows the results of the sampling of the carbon dioxide emitted in the same
experiment [39]. As the percentage of hydrogen expressed as molar fraction increases (0,
pure methane; 1, pure hydrogen), the carbon dioxide content drops until it reaches zero
when the mixture is made up of only hydrogen and air. The results are in agreement with
the chemiluminescence emission described later in Figures 11 and 12. As expected from the
numerical calculation data in Figure 1, the presence of carbon dioxide is significant, even at
very high H2 mole fraction values.
Energies 2023, 16, 7174 11 of 29

Figure 8. CO2 concentration at varying hydrogen contents (the molar fraction is reported on the
horizontal axis) in the premixed CH4 /H2 /Air Bunsen flames studied in [39].

2.3. Effects on Radiant Energy Transfer

Radiative transfer of energy (RTE) is a highly significant mechanism in a multitude of
applications, including high-pressure and high-temperature engine combustion chambers,
rocket propulsion, hypersonic vehicles, spacecraft atmospheric reentry, ablating thermal
protection systems, glass manufacturing, plasma generators, and nuclear fusion.
It is important to note that hydrogen flames are notably less visible compared to flames
produced by natural gas. This reduced visibility is a result of the lower concentration of
radiant species, including soot, CO2 , and radicals in hydrogen flames. Consequently,
detecting these flames presents a more intricate challenge. Infrared flame detection meth-
ods are ineffective for hydrogen flames, necessitating the use of ultraviolet systems, as
discussed in [53–56].
At the same time, this also affects the radiative heat transfer from the flame, with
important implications in some applications, such as glass furnaces. The lower emissivity
and lower mass flow rate (less air is required while increasing the H2 content to generate a
flame comparable to natural gas, i.e., with the same heat release) of the combustor, therefore
changing the heat transfer balance.
The radiative absorption properties hinge on the absorption coefficient, denoted by κλ .
In gases, this coefficient often exhibits significant variations with respect to wavelength,
temperature, and pressure. It also increases in direct proportion to the concentration of
participating species. While solid surfaces can generally be assumed as opaque, the absorp-
tion or emission properties of gases exhibit irregularities within the wavelength domain,
becoming particularly noteworthy at temperatures below a few thousand Kelvin. As the
temperature increases, the absorption coefficient for cold lines diminishes, but hot lines
emerge at higher wavelengths, slightly increasing the absorption coefficient. Elevating
the pressure results in spectral line broadening, primarily due to molecular collisions [57].
This broadening leads to wider and more overlapping lines, especially at higher pressures,
rendering the gas more “gray” or opaque. Consequently, the amplitude of the spectral
absorption coefficient significantly increases, as depicted in Figure 9 and as also reported
in [58,59] (p. 138). An appropriate and practical average absorption coefficient for character-
izing the total emission from a volume element within an absorbing medium is the Planck
mean absorption coefficient. This coefficient solely depends on local properties and can
be tabulated. Presently, the Planck mean absorption coefficients, which were estimated in
the past [57] (pp. 253–324), can be more accurately computed directly from high-resolution
spectroscopic databases, such as HITRAN [60] and HITEMP [61], as demonstrated in the
study by [62]. The newer databases tend to yield absorption coefficients that are generally
Energies 2023, 16, 7174 12 of 29

higher than those obtained using older databases, particularly at higher temperatures and
pressures: Figure 9 (bottom right) shows this effect for carbon monoxide.

Figure 9. The carbon monoxide (CO) absorption coefficient at 800 K and different pressures (top
and bottom left), and the related mean Planck absorption coefficient versus temperature (bottom
right). Calculations were performed by means of the HAPI code [63] using the HITRAN [60] and
HITEMP [61] high-resolution spectroscopic databases, with the Voigt model assumption for the line
shape.

At the temperatures typically encountered in industrial furnaces and combustion

chambers, the gaseous species that play a significant role in absorbing and emitting radia-
tion are carbon dioxide (CO2 ), water vapor (H2 O), carbon monoxide (CO), sulfur dioxide
(SO2 ), nitrogen oxide (NO), and methane (CH4 ). Other gases, such as nitrogen (N2 ), oxygen
(O2 ), and hydrogen (H2 ), are essentially transparent to infrared radiation and do not signif-
icantly contribute to emission or absorption. However, their importance as absorbing and
emitting contributors becomes pronounced at extremely high temperatures. Furthermore,
a noteworthy contribution to radiation is also derived from hot carbon particles, commonly
referred to as soot, within the flame, as well as from suspended particulate material, as is
the case in pulverized-coal combustion processes.
Regarding flames, it is well established that disregarding radiation under atmospheric
pressure conditions can result in an overestimation of temperature by as much as 200 K.
Energies 2023, 16, 7174 13 of 29

However, it is important to note that numerical predictions are highly dependent on

the radiative transfer of energy (RTE) model employed. The commonly used optically
thin or gray radiation models tend to underestimate the temperature by up to 100 K or
more, as discussed in [64,65]. Moreover, radiation is intensified by turbulence through
strong nonlinear interactions between fluctuations in temperature and radiative properties
(TRI). These interactions lead to increased heat loss from a flame, resulting in a local gas
temperature reduction of 200 K or more. This TRI cooling effect is even more pronounced in
high-pressure combustors, which typically exhibit greater optical thickness, as highlighted
in [66,67].
In systems where RTE is a significant factor, it has been demonstrated that radia-
tion can be considered equivalent to a substantial nonlinear diffusion term. In fact, the
transfer of heat through radiation can function as a preheating mechanism, similarly to
heat conduction. As a result, this preheating effect contributes to higher flame speeds, as
discussed in the work by Mercer in [68]. As an example, Figure 10 shows an instantaneous
distribution of the radiative source term in the energy equation in a non-premixed cyclonic
combustor [69] burning air and hydrogen in a MILD combustion regime. The source term is
estimated by means of the M1-radiation model [70]: its distribution reveals regions exhibit-
ing heat losses (negative radiative source term) or preheating effects (positive source). The
distribution of the radiative source term versus temperature is also shown at the bottom
of the same figure, colored by means of the OH radical mass fraction: regions reacting at
higher temperatures with higher OH concentrations lose heat, while colder non-reacting
regions (jets, identifiable in the planar section of Figure 10, top) with lower OH contents
are preheated.

Figure 10. Instantaneous spatial distribution on a planar section of a cyclonic combustor burning
hydrogen and air in non-premixed MILD combustion regime [69]. The distribution shown at the
bottom is colored by means of the OH radical mass fraction.

When it comes to the peak flame temperature, radiation typically reduces it in low-
pressure flames. Although radiation effects become more pronounced with increasing
pressure, primarily due to the heightened emission and absorption of energy, the peak
flame temperature is less affected by radiation. This is attributed to the faster chemical
reactions that occur at higher pressures, a phenomenon also observed in [58] (p. 139). In
fact, based on the Arrhenius law, the chemical reaction rate is directly proportional to the
molar concentrations of the reactants raised to a power that corresponds to the number
Energies 2023, 16, 7174 14 of 29

of moles required to collide for the reaction to take place. As a result, the reaction rate is
directly proportional to pressure (p) for first-order reactions and to the square of pressure
(p2 ) for second-order reactions. Three-body reactions are even more greatly influenced by
pressure, as indicated in [71].
It is known that hydrogen flames have a lower emissivity than natural gas flames. Such
radiative emission changes may have important implications in some applications [72].
In [39], a series of premixed Bunsen flames at a constant thermal power of 7.1 kW,
burning methane and hydrogen in air at atmospheric pressure with increasing hydrogen
content, were experimentally investigated. While increasing the hydrogen content, the
thermal power was kept constant, maintaining the same laminar flame speed of the fuel
mixture (hence, decreasing its equivalence ratio) and increasing the flow rate (hence, the jet
Reynolds number). The spectrum of the electromagnetic radiation emitted was measured
in a range of wavelengths between 200 and 1080 nm (nanometer), from ultraviolet to near
infrared. The radiation emitted was collected by a system of lenses capable of focusing
the image of the flame in an area of about 1–2 cm, where it was collected by an integrating
sphere and sent, through an optical fiber, to a digital spectrometer. The integrating sphere
is a spherical device which has the ability to concentrate almost all of the radiation collected
inside it through a hole of about 1 cm made on its surface: measurement details can be found
in [39,73]. The result is that, by integrating the measurement over a rather large surface of
flame, the spatial dependence of the measurement is substantially lost, highlighting the
spectral dependence on the wavelengths and the type of mixture.
Figure 11 shows the spectra of radiant energy emitted by flames in [39] with increasing
hydrogen contents. The arrow with X H2 defines the direction in which the molar fraction
of hydrogen in the methane/air mixture increases. It starts from a pure methane flame, up
to a pure hydrogen flame. The figure also shows the spectral emission lines of the major
emitting species. As the carbon content in the mixture decreases, the decrease in energy
emitted by the species CH, CO2 , C2 , H2 O, and H2 is evident.

Figure 11. Emission spectrum at different hydrogen contents in the premixed CH4 /H2 /Air Bunsen
flames studied in [39]. The X H2 (hydrogen the molar fraction) arrow points to the increasing direction
of the hydrogen molar fraction.

As the hydrogen content in the mixture increases, the contribution of carbon to the
emission of radiative energy progressively decreases until, in the mixture of pure hydrogen,
only the emission peak of water and H2 survives, strongly reducing the ratio between
radiant/convective energy emitted. In all mixtures, the emission peak of the OH radical,
located in the ultraviolet around a wavelength between about 260 and 310 nm, is sub-
stantially absent, despite being a chemical species strongly present inside the flame front.
According to the authors in [39], the reason for this absence could lie in the low sensitivity
of the instrument at those wavelengths, such as to return a signal-to-noise ratio that is too
Energies 2023, 16, 7174 15 of 29

low for this type of measurement. Even with this lack, the differences in radiant energy
emitted with the presence or absence of methane are considerable.
A lower radiative emission translates into a greater quantity of energy which is trans-
mitted by convection, which mainly follows an axial direction, whereas the radiative one is
emitted in all directions, and, given the cylindrical symmetry of the flame, preferentially in
a radial direction. While this is beneficial for gas turbine applications (lower heat losses to
walls and less cooling issues), it could be a serious issue in other industrial applications
such as raw-material melting kilns or product cooking kilns.
In the same experiments [39], the temperature of a strongly absorbing metal body
(black colored) positioned on the flame side at a distance of about 2 diameters D (D, the
diameter of the Bunsen burner adopted) was measured by a thermocouple. The correlation
between the radiant energy emitted in the radial direction and temperature is shown in
Figure 12. It can be seen that, as the hydrogen content increases, the value of the integral of
the radiative emission (I) is linearly anti-correlated with the temperature reached by the
absorbent body. It can be deduced that the reduction in the chemical species that emit by
chemiluminescence strongly influences the amount of radiative thermal energy emitted. It
is also observed that up to a hydrogen volume content of 78% (30% by mass of hydrogen),
this phenomenon is strongly limited: even a minimal quantity (in volume) of methane is
sufficient to “color” the flame, which emits over a more extensive range of wavelengths;
the flame is instead almost colorless when the carbon is absent.

Figure 12. Integrated emission spectrum (over all wavelengths) for the various hydrogen contents
vs the temperature measured in the radial direction for the premixed CH4 /H2 /Air Bunsen flames
studied in [39]. Each experimental point is labeled with molar fraction of hydrogen. See Figure 1 for
the equivalence between hydrogen mass and volume fraction.

2.4. Effects on Materials

Besides affecting combustion characteristics, hydrogen enrichment to natural gas
also affects materials. Hydrogen can be absorbed by certain containment materials and
piping, potentially leading to the loss of ductility or embrittlement in them. Hydrogen
embrittlement becomes evident shortly after its introduction into a system and is an irre-
versible process. This phenomenon diminishes the material’s yield stress, consequently
compromising its fatigue resilience, particularly under low-cycle fatigue conditions [74].
The extent and rapidity of embrittlement is accelerated by factors such as high temperature,
pressure, and stress levels. It is important to note that not all materials exhibit the same
susceptibility to hydrogen embrittlement. Stainless steels and nickel alloys, which are fre-
quently employed in gas turbine combustion systems, are particularly prone to heightened
embrittlement at elevated temperatures. This complicates the selection of materials for
Energies 2023, 16, 7174 16 of 29

combustion hardware, weld joints, and braze joints due to the need to mitigate the effects
of hydrogen embrittlement.
A 100% hydrogen flame is typically shorter and positioned much closer to the burner
when compared to a methane flame operating under the same conditions. This difference
is primarily due to the higher flame speed and shorter ignition times associated with
hydrogen, as highlighted in [37]. Conversely, industrial experience has shown that, when
high percentages of water or steam are added to the fuel, the flame length can significantly
increase. This, in combination with the elevation of flame temperature, carries important
implications for the potential impact on combustor materials, as discussed in [75]. The most
significant worry concerning hot gas path components arises from the fact that hydrogen’s
elevated combustion temperature leads to a rise in turbine firing temperature. Furthermore,
the gas temperature profile upon leaving the combustor will be hotter and exhibit distinct
characteristics when burning hydrogen in comparison to natural gas. This heightened firing
temperature and alterations in the combustion profile shape will necessitate modifications
in the designs of component cooling and coatings to avert any reduction in part lifespan.
It is also crucial to take into account that the combustion of hydrogen results in a
change in the composition of the exhaust gases compared to the use of natural gas. This
alteration in the composition of combustion products can have a notable impact in direct
combustion equipment, particularly in situations where the combustion gases directly
interact with the products being produced, as mentioned in [76,77]. In cases where direct-
fired equipment mixes flue gases with significant amounts of fresh air before they come
into contact with the product, such as in dryers operating at approximately 200 °C, this
is less likely to be a major issue. However, further testing is advisable to confirm this. In
contrast, in certain applications like glass kilns or lime kilns, where the flue gases are not
mixed before they contact the product, changes in flue gas composition could potentially
affect the quality of the product itself, for instance, by influencing the volatility of sulfate in
glass furnaces, as discussed in [77]. A particular concern is the increased moisture content
of flue gases [77] and the potential consequences this might have within furnaces and other
direct-fired equipment, as highlighted in [72].

3. Gas Turbine and Piston Engines Power Generation

Although natural gas currently stands as the most environmentally friendly option
among major combustion fuels, employing it contributes to roughly 20% of the total CO2
emissions, with nearly 15% for power generation in the United States [78]. Hydrogen is
a viable fuel option for both reciprocating gas engines and gas turbines to reduce CO2
emissions, but its use in power generation is negligible at present, accounting for less than
0.2% of the electricity supply [1].

3.1. Hydrogen Piston Engines

Hydrogen can be effectively employed in piston engines when blended with hy-
drocarbons, utilizing fuel and injection systems similar to conventional gasoline engines.
Consequently, hydrogen-powered vehicles represent a promising way to diminish the
reliance on fossil fuels within the automotive sector; a history of hydrogen combustion
vehicles can be found in [79].
Some of the already mentioned properties of hydrogen in Section 2 can have a positive
impact on the use of H2 as fuel in piston engines: its wider flammability range; its very
low ignition energy (an order of magnitude less than gasoline); its high octane number
(due to the self-ignition temperature being higher than gasoline), above 130, offering a
high resistance to knocking combustion [80]; its high diffusivity, facilitating the formation
of uniform fuel–air mixtures; its high flame speed (an order of magnitude higher than
gasoline); and injected in a gaseous state, it provides optimal cold start performance. Some
other features can have negative impacts: since the quenching distance is smaller than
that of gasoline, the flame can propagate closer to the cylinder, causing serious flashback
problems when reaching the inlet valve; due to the very low density of hydrogen, storage
Energies 2023, 16, 7174 17 of 29

tanks can result in volume problems, and the energy density of the air/hydrogen mixture
and, therefore, the power is reduced.
Using hydrogen as a fuel in piston engines requires significant engine modifications,
particularly in the areas of fuel–air mixture injection, compression, and ignition.
The mode of injection plays a crucial role in influencing airflow distribution, impacting
the mixing and combustion of hydrogen and air. For hydrogen, direct high-pressure or
low-pressure injection (depending on the phase of the cycle) is considered the optimal
choice [80–82]. This method involves injecting fuel with the intake valve closed, reducing
the risk of premature mixture ignition and preventing backfires in the delivery channel.
However, injecting hydrogen into the intake port can lead to airflow blockage, potentially
decreasing engine power and even causing engine shutdown, especially when higher
hydrogen levels are required for increased power. Attempts to enhance power through
supercharging introduce challenges such as increased risk of hot spot formation, backfires,
and pre-ignition, which require leaner fuel ratios, limiting potential power gains.
Achieving the highest efficiency with hydrogen in piston engines might necessitate
a higher compression ratio compared to gasoline engines [83]. This is because the self-
ignition temperature of hydrogen is higher. The temperature increase during compression
is directly linked to the compression ratio, so a higher self-ignition temperature permits a
higher compression ratio, and this, in turns, improves efficiency.
Regarding spark plugs, they must prevent the electrode temperature from exceeding
the ignition threshold and causing backfires. It is worth noting that platinum electrode
spark plugs are not suitable for hydrogen use [83], as their catalytic properties could
encourage hydrogen oxidation.
Direct injection [82] prevents flame propagation within the intake circuit but may not
necessarily prevent pre-ignition inside the combustion chamber. To address pre-ignition
issues, techniques like exhaust gas recirculation (EGR) are employed to introduce thermal
dilution [84]. EGR helps lower the temperature of hot spots, reducing the chances of
pre-ignition. Additionally, this method decreases combustion temperature peaks, leading
to a reduction in NOx emissions.
Compared to gasoline vehicles, hydrogen-powered vehicles can produce equivalent
or even up to 20% higher levels of NOx emissions. However, the use of a selective catalytic
reduction (SCR) system can effectively reduce NOx by catalytically decreasing nitrogen
oxides in the exhaust gas, employing ammonia as a reducing agent.
Although the most advanced gas-reciprocating (or piston) internal combustion engines
are capable of accommodating gases containing hydrogen content of up to 70% on a
volumetric basis [85] and several manufacturers have showcased the feasibility of engines
that operate using 100% hydrogen (anticipated to become commercially accessible in the
near future), they can be generally fed with a fraction of about 30%, going beyond 50% by
adjusting the compression and power in some cases. The main problems are the increased
explosion limits and tendency to detonate, and the increased size of the fuel injection
system, which can lead to a downgrading of engine displacement by more than 30%. Other
issues include increased NOx emissions. This may require the installation of catalytic
exhaust systems, which are already used in some gas engines.
The major manufacturers of hydrogen piston engine vehicles include brands such
as: Ford, BMW, Mazda, Chevrolet and Toyota. The characteristics of these engines can
be found in [79]. Just as an example, Figure 13 reports Mazda’s RX-8 Hydrogen RE, an
intriguing solution featuring a hydrogen Wankel rotary engine [86]. This engine is supplied
with hydrogen gas through an electronically controlled direct injection system. The use
of a Wankel rotary engine offers a notable advantage in this context. This engine design
employs separate chambers for induction and combustion, which helps mitigate the issue
of backfiring commonly encountered when using hydrogen in piston engines.
Energies 2023, 16, 7174 18 of 29

Figure 13. Mazda’s RX-8 Hydrogen RE hydrogen Wankel rotary engine [79,86].

3.2. Hydrogen Gas Turbines

Thermo-electric power generation with gas turbines is one of the most immediately
applicable solutions for reducing CO2 emissions. However, a significant share of CO2
emissions in the power generation sector can be attributed to gas turbines: utilizing hy-
drogen combined with natural gas will progressively become more significant in the effort
to decrease CO2 emissions. While renewable energy sources are making progress on the
global energy stage, gas turbines will maintain their prominence in power generation both
during the energy transition period and in the future energy scenario with an increasing
percentage of non-programmable renewable sources, thanks to their capability to provide
flexibility to the electric grid system [87,88]. In this vision, it has to be accepted that, over
the years, the very concept of the gas turbine will undergo a natural evolution, adapting to
the technological advances offered by the market. The flexibility of gas turbines gathers
both their “load-flexibility” or “operational flexibility”, and their “fuel-flexibility” [89].
Load flexibility, in the context of gas turbines, pertains to the turbine’s ability to swiftly
adjust its power output, contributing to the rapid stabilization of the electric grid. Various
solutions have been suggested and put into practice in recent years, as noted in [90–92].
These efforts have resulted in the achievement of a power ramp rate of 10% of the nominal
power per minute, which appears to be satisfactory for gas turbine users at present. This
capability should be maintained as we transition to hydrogen gas turbines in the future.
Fuel flexibility, on the other hand, relates to a gas turbine’s capacity to operate effectively
with various types of fuels, and more specifically for the present time, with fuel blends
with a varying hydrogen content [93]. However, despite the considerable efforts and in-
vestments made by various manufacturers in recent years, the actual fuel-flexibility of the
machines, i.e., their stable, efficient, clean, reliable, and safe operation from 100% natural
gas to 100% hydrogen with varying hydrogen content, is a challenge yet to be overcome
due to technological issues in the combustion system.
Hydrogen significantly modifies the combustion characteristics of a reacting mixture
in comparison to natural gas. Specifically, the following changes are observed: a decrease
in the ignition delay time; the enlargement of flammability limits; an increase in laminar
flame speed; an increase in turbulent flame speed, which also becomes more pressure-
dependent [94,95]; an increase in the adiabatic flame temperature. Hence, apart from issues
related to its production, storage (lower vapor density), and transportation, safety issues
also arise from such changes. In particular, the broader flammability range amplifies the
potential for fuel ignition within the mixing passages; combustion dynamics can be dra-
matically affected by dangerous flashbacks due to the increased flame speed [96] and/or
thermo-acoustic instabilities [97,98] that can lead to unexpected maintenance interven-
tions, consequently diminishing the overall system’s reliability. Despite extensive research
and industrial efforts over the years, the issue of combustion instability remains partially
Energies 2023, 16, 7174 19 of 29

unresolved. The strategies typically employed to mitigate the potentially hazardous conse-
quences of these instabilities in modern gas turbines primarily rely on empirical methods.
Furthermore, the impact of hydrogen content on combustion dynamics has raised concerns
about the reliability of the Wobbe index as a measure of fuel interchangeability, as discussed
in [99]. During transient operations, such as start-up and shutdown, these dynamics be-
come a primary concern. The implementation of advanced sensors for real-time combustion
monitoring can be a key requirement [100,101]. For the foreseeable future, the inclusion
of a safe fuel like natural gas will remain necessary for non-steady operations such as
startup, shutdown, and part-load scenarios. Startup procedures typically rely on natural
gas or liquid fuels, often involving a combination of diffusive and premixed combustion, at
least up to the full-speed no load (FSNL) condition. Currently, it is generally acceptable to
include an average volume that is 5% hydrogen during the startup phase. In essence, the
stable operability window for many lean premixed combustors becomes narrower due to
these dynamics.
Controlling temperature peaks to restrict NOx emissions requires special consideration.
Keeping these peaks below the existing natural gas limits of 25 parts per million by volume
(ppmv) seems to be a challenging endeavor for gas turbines operating within the 0–100%
hydrogen range until 2030. Achieving this goal is difficult because higher temperatures can
be easily reached in the process. It has been observed that hydrogen changes the exhaust
gas composition (more water) and that the gas turbine power should also be considered.
For these reasons, there is an open discussion in gas turbine associations and OEMs about
how to take into account such operating conditions in the law limits: a very promising
suggestion to discuss with regulatory entities is to quantify such emissions as the ratio
between the mass of NOx at the exit and the input fuel energy (mg/MJ) [102].
Burning fuel mixtures with a high hydrogen content also has another significant
impact—an increase in the steam content within the exhaust gases. This, in turn, leads to
heightened heat exchange in the hot section of the gas turbine, necessitating additional
cooling, as mentioned in [103]. However, this increased exposure to steam also raises con-
cerns about hot corrosion and shortens component lifecycles. To address these challenges,
a commonly adopted solution is to reduce the turbine inlet temperature, which results in a
reduction in the machine’s power output. While this approach can help mitigate the risk of
hot corrosion, it comes at the cost of a 2% point reduction in efficiency, making it another
challenging aspect to maintain until 2030, as discussed in [104].
Furthermore, for a fixed heat release, using a blend with 100% hydrogen necessitates an
extra volumetric flow of fuel, approximately three times more than that needed for methane,
making the direct and seamless utilization of hydrogen in gas turbines challenging.
In the end, necessary modifications in design are highly contingent on the proportion
of hydrogen intended for combustion. The utilization of hydrogen can be categorized into
groups based on the volume percentage: low (5–10%), medium (10–50%), and high (more
than 50%) blends. Turbines operating with a low hydrogen blend may not necessitate
design alterations, as the fuel-burning characteristics closely resemble those of a pure
natural gas stream. In the case of medium blends, the overall architecture and combustor
of the turbine might remain largely unchanged, but adjustments to combustor materials,
fuel nozzles, and control systems will be essential. The development of retrofit solutions
for existing gas turbines is certainly a key factor. When dealing with higher hydrogen
blends exceeding 50%, extensive modifications to the turbines become imperative, and a
comprehensive retrofit of the combustion system is likely required. Numerous original
equipment manufacturers (OEMs) are presently engaged in developing new combustion
systems capable of accommodating elevated hydrogen blend levels.
Hence, as the proportion of hydrogen in the fuel increases, an unmodified combustion
system encounters greater challenges. Compounding these difficulties, in the foreseeable
future, combustion systems will need to retain both fuel flexibility and the capability to
burn natural gas.
Energies 2023, 16, 7174 20 of 29

While research is very advanced for low levels of hydrogen, it is significantly less so
for high levels. The state of the art on hydrogen combustion is based on two combustion
modes: diffusion flames with nitrogen, water or steam as diluent and lean premixed flames.
In combustion systems utilizing a diffusion flame and the addition of diluents, it is
feasible to accommodate up to 100% volume of hydrogen. Nevertheless, such systems
come with several drawbacks. These include reduced efficiency when compared to systems
that do not use dilution, elevated levels of nitrogen oxides (NOx ) in comparison to lean
premix technology, increased plant complexity, and consequently higher construction and
maintenance costs.
Dry premixed combustion technology (dry low-emission, DLE, or dry low NOx , DLN)
does not implement any dilution; it is typically lean premixed or partially premixed to
enable the better control of temperature and NOx emissions. Effective mixing is essential
for the abatement process. However, achieving the right residence times and sufficient
volumes can be challenging to prevent self-ignition or flashback. In the lean premixed
combustion, fuel and hot air mix in the mixing area but do not react until they enter the
combustion chamber. It is important to note that these combustion strategies are prone to
dangerous thermo-acoustic instabilities, especially near lean quench conditions. DLN/DLE
combustion technologies can be categorized into four groups based on the approach used to
stabilize combustion: combustion aerodynamically stabilized by propagation; combustion
stabilized by self-ignition; staged combustion, stabilized using various methods (including
propagation and self-ignition); micro-mixing combustion, involving multiple small flames
that can be premixed, partially premixed, or diffusive. A comprehensive review of DLE
gas turbine combustion technologies for hydrogen blends can be found in [69].
DLN/DLE combustion technology has greater potential than non-premixed and di-
luted combustion, but is not yet mature enough for very high hydrogen contents or when
the greater flexibility of the fuel mix is required (e.g., to use natural gas/hydrogen mixtures
with an H2 content of 0–100%). The maximum permissible hydrogen concentration varies
widely between manufacturers. Table 1 shows the levels of hydrogen currently accepted
by the different classes of gas turbines [105,106], from heavy-duty, to industrial, to aero-
derivative and microturbines (20% vol. H2 refers to the lowest powers). The rationale
behind these variations lies in the differences in combustion temperatures and the technolo-
gies employed within these distinct classes of gas turbines. When it comes to micro-gas
turbines, despite the endeavors of certain original equipment manufacturers (OEMs), they
do not progress along the learning curve at the same rate as their heavy-duty counterparts.
This is mainly due to their limited tolerance for hydrogen. However, given that users
of micro-gas turbines often rely on the same gas grid as larger turbines, it is essential to
dedicate more efforts to research and development to attain a comparable level of hydrogen
compliance.

Table 1. State of the art for gas turbines on the volume percentage accepted by the combustor [105].

Combustion H2 % Vol. NOx |Complexity|CAPEX/OPEX

Non-premixed/diluted 0–100% Higher
∼44–63% heavy duty (100–500 MWe)
∼43–55% industrial (30–100 MWe)
DLE lean premixed comb.
∼35% aeroderivative (1–30 MWe)
∼20–32% microturbine (0.1–1 MWe)

Currently, there are no fuel-flexible DLE machines on the market capable of handling
the entire 0–100% range of hydrogen mixed with natural gas. The technical experience
accumulated with high hydrogen syngas (30 and 60% vol. of H2 and CO), revisited and
adapted, has proved useful. As a result, most gas turbine manufacturers offer units origi-
nally developed for syngas applications, which can also be used for natural gas/hydrogen
mixtures with high H2 levels (around 60% vol.). When examining the catalogs of OEMs,
the current state-of-the-art in dry low emission (DLE) gas turbines reveals the capability to
Energies 2023, 16, 7174 21 of 29

burn hydrogen up to an average of 30% by volume while maintaining low NOx emissions
(below 25 ppmv at 15% oxygen). Due to the higher flame temperatures associated with
hydrogen compared to natural gas, some cases control NOx emissions solely by reducing
the machine’s power output, a practice known as derating, as discussed in [106]. It is worth
noting that the strictest NOx limits for natural gas (less than 15 ppmv at 15% oxygen) are not
consistently met today. For instance, Ansaldo Energia GT36 and GT24/GT26 (as shown in
Figure 14) gas turbines can accommodate up to 50% and 30% hydrogen by volume while
still complying with the 15 ppmv limit, whereas AE94.3A and AE94.2 turbines can tolerate
up to 25% hydrogen by volume while meeting the 25 ppmv compliance. As a result, a
significant portion of investments are focused on DLE technology [69], specifically lean
premixed combustion without dilution (e.g., steam, nitrogen, water), even for retrofit so-
lutions. Moreover, new combustion concepts are being explored, including sequential
combustion at constant pressure (as implemented in the GT36) [90,107], micro-mixing-
based approaches [108], and exhaust gas recirculation (EGR) techniques [5,6].

Figure 14. Section of the GT24/GT26 gas turbine illustrating the concept of sequential combustion [90].

Table 2 shows the key performance indicators (KPIs) for DLE gas turbines with
reference to the state of the art (SoA) in 2020 and with forecasts to 2024 and 2030. It is
noted that maintaining the same NOx limits from 30 to 100% H2 is already a challenge;
moreover, the commonly adopted normalization for NOx to 15% O2 under dry conditions
(without H2 O) cannot be applied to fuels with very different reactivity and combustion
products than natural gas; a more appropriate normalization is that suggested in the
same table, which uses the mass of NOx in mg per quantity of fuel energy injected in
MJ; this new normalization was suggested not only in the SRIA2021-2027 of the Clean
Hydrogen Partnership [105], but also in the Hydrogen Working Group of the European
Turbine Network [15]. As far as a start-up is concerned, it should be noted that this phase
is typically carried out with only natural gas or liquid oil.

Table 2. Key performance indicators for DLE gas turbines [105]. NOx refers to NO + NO2 . The
maximum electrical efficiency loss refers to the full-speed full-load condition in combined cycle gas
turbines. The minimum ramp rate is referred to the full-load condition.

KPI Unit SoA 2020 Target 2024 Target 2030

% by mass 0–5 0–23 0–100
H2 fuel content
% by volume 0–30 0–70 0–100
ppmv at 15%O2 dry <25 at 30% vol. H2 <25 at 70% vol. H2 <25 at 100% vol. H2
NOx emissions
mmg/MJfuel <31 at 30% vol. H2 <29 at 70% vol. H2 <24 at 100% vol. H2
% by mass 0.7 3 100
Max. H2 content at start-up
% by volume 5 20 100
Max. electrical efficiency loss % points 10 at 30% vol. H2 10 at 70% vol. H2 10 at 100% vol. H2
Min. ramp rate % load/minute 10 at 30% vol. H2 10 at 70% vol. H2 10 at 100% vol. H2
% by mass/minute ±1.4 ±2.21 ±5.11
H2 accepted fluctuations
% by volume/minute ±10 ±15 ±30
Energies 2023, 16, 7174 22 of 29

4. Hard-to-Abate Industry
Constituting 38% of the total final energy demand, the industrial sector stands as the
most substantial end-use segment. Notably, this sector is responsible for 26% of the global
energy system’s CO2 emissions [1]. Involving processes heavily relying on fossil fuels,
the hard-to-abate sector is the most challenging in reducing pollutant emissions [72,109]:
electrification is not a straightforward solution in most related industrial processes and
the potential implementation of hydrogen opens some critical issues regarding the process
itself and the quality of the product. Within the industrial landscape, hydrogen plays a role
in utilizing 6% of the overall energy demand. This hydrogen is predominantly employed as
feedstock in chemical production and as a reducing agent in the manufacturing of iron and
steel. The annual industrial demand for hydrogen amounts to 51 million metric tons [1].
Table 3 reports combustion-based applications in the hard-to-abate sector.

Table 3. Combustion applications for the hard-to-abate sector, related processes, and equipments.

Applications Processes Equipments

Food Hot water production, steam production, drying Boiler, cogeneration, direct flame oven, dryer
Steam production, drying, cracking, direct heat at high
Chemicals Boiler, cogeneration, direct flame oven, dryer
temperature
Varnishing, environmental heating, drying, hardening,
Vehicle production Boiler (also at high pressure), direct flame oven, dryer
welding, pressing
Steel lamination and melting, melting of non-ferrous
Metals Various type of ovens
metals, thermal treatments
Distillation, reforming, isomerization, cracking,
Refining calcination, hydro-treatment, catalyzer regenaration, Oven, boiler, cogeneration
steam production
Hot water production, steam production, drying, refining,
Paper Boiler, cogeneration, direct flame dryer
finishing
Raw material melting, conditioning, annealing, molding,
Glass Gas oven for melting, annealing oven
pressing
Gas oven, dryer with recuperated heat, boiler for hot
Ceramic Cooking of raw materials, drying, molding, finishing
water
Lime kiln: regenerative (parallel fluxes) or vertical kilns
Cement Cooking of raw materials
(older)
Non-metallic minerals Drying, melting, calcination, evaporation, separation gas dryer, oven, boiler, CHP

Producers sell burners (generally working at atmospheric pressure) able to operate up

to 100% H2 usually in the chemical or refining sectors, where a subproduct of hydrogen
is produced. Due to the high flame temperature, combustors’ material have to be chosen
suitably. In fact, the flame can easily attach close to the nozzles, making the choice of
materials a serious concern. High-frequency noise can be avoided by means of silencers
or damping devices. Some burners operating at 100% H2 are non-premixed to reduce
NOx (for example, in the MILD or flameless combustion regime); others are DLE/DLN
premixed. There exist burners without flashback up to 100% H2 .
Almost all glass is produced in furnaces where a mixture of raw materials is combined
and melted into a homogeneous mixture. Like many industrial production processes, glass
melting can be classified as a continuous or discontinuous (batch) process. The melting
point of most glass is around 1400–1600 °C, depending on its composition. Consequently,
glass production requires a large amount of thermal energy. Because of this high energy
demand, glass furnaces are built to minimise heat loss and often feature some form of waste
heat recovery system: regenerative, recuperative, electrical. The most commonly used fuels
for glass melting furnaces are natural gas, light and heavy fuel oil, and liquefied petroleum
gas. Methods are currently being investigated to increase the radiative qualities of hydrogen
to make it a more viable alternative to natural gas. Traditionally, pure hydrogen has been
considered unsuitable for glass melting. This is because the heat produced by its flame is
Energies 2023, 16, 7174 23 of 29

unable to penetrate the liquid glass bath well, leaving the top layer too hot and the bottom
too cold. It has always been thought that a glass furnace requires a ‘sooty’ flame to function,
as soot improves the radiant heat transfer. Moreover, existing hydrogen combustion
systems have not proved suitable for rapid implementation in existing melting furnaces,
as major changes in the composition of the furnace atmosphere are expected [72,77]. The
influence of these variations on glass chemistry has not yet been adequately studied.
For the lime industry, in the most advanced dry process, raw materials are calcined at
around 900–1250 °C in a pre-calciner to transform the limestone into lime, which releases
CO2 as a by-product. The materials are then fed into a rotary kiln, where they aggregate to
form clinker at 1450 °C with flame temperatures reaching 2000 °C. The fuel can be coal gas
or hydrogen-rich syngas. In the lime industry, the water content of the flue gas would pose
a significant challenge [72]. Calcium oxide in fact reacts with steam, causing problems with
the quality, efficiency, durability, and safety of the product.
Besides being used as a reducing agent, hydrogen has great potential as a fuel in
the steel production process. The possible applications of hydrogen mainly concern the
production of pellets, the sintering process, reheating, and heat treatment furnaces. Several
manufacturers of combustion systems for the steel industry already market some MILD or
flameless type furnaces, which have been successfully tested with a variety of mixtures of
natural gas and hydrogen, up to 100% hydrogen. In the MILD combustion mode, the heat
release is distributed over a large volume, ensuring an even heat distribution, which is very
effective for the material being processed. Products available on the market include, for
example, TENOVA’s TSX series [110] of reheating furnaces with NOx emissions below 80
mg/Nm3 at 5% O2 , with a furnace temperature of 1250 °C; in 2022, TENOVA also built the
first industrial furnace with TRKSX combustion systems [111] for heat treatment in MILD
mode up to 100% hydrogen, with NOx emissions compatible with future, more stringent
regulatory limits. Among other applications, LINDE also invested in oxy-combustion,
which can reduce both energy consumption and emissions [112]; in 2020, it tested a full-
scale MILD oxy-combustion reheating furnace in Sweden with up to 100% hydrogen with
its REBOX HyOx combustion system [113].
Roller kilns are commonly utilized in the ceramics industry because of their efficiency
in achieving temperature variations. They achieve this by moving the product through
zones of different temperatures along the length of the kiln, rather than periodically heating
and cooling the entire kiln. Additionally, they enhance productivity by allowing for
continuous production. In the ceramics industry, industrial kilns used for ceramic tile
production are predominantly of the roller type, typically fueled by gas. These kilns can be
quite extensive, reaching lengths of up to 300 m, and they may have several hundreds of
burners positioned along their length. Depending on the specific type of production, these
kilns must be capable of maintaining temperatures of up to 1250 °C, while it is preferable
to keep the silicon carbide (SiC) burner tubes, which contain the flame, at temperatures
below 1300 °C. Fuels can be natural gas, LPG, diesel, paraffin, and other liquid fuels up to
temperatures of 1800 °C. In the case of hydrogen, the great challenge concerns the moisture
content of the combustion gases, since the ultimate goal of ceramic production is to remove
moisture [114].
The use of hydrogen in boilers [115] is common in those sectors where hydrogen
is a waste product of chemical processes. Consequently, there are a number of known
technological measures for its safe and efficient handling. This particularly concerns piping,
nozzles, and high-temperature resistant components that come into contact with flames,
burner fans, and the combustion chamber. A 100% hydrogen-fueled boiler can be up to
10% larger than a natural gas boiler producing the same output. Flue gas recirculation is
generally used to lower the average flame temperature and contain NOx . To prevent the
ignition of the mixture in the supply line, the system is equipped with upstream flame
breakers. In steam boilers [116], when switching from natural gas to hydrogen, the variation
in heat absorption between the radiant/convective sections can be mitigated by regulating
the feedwater split between the two sections.
Energies 2023, 16, 7174 24 of 29

Table 4 briefly compares the applications described above and the barriers/problems
for using hydrogen in the device considered.

Table 4. Main applications of the hard-to-abate sector and barriers to hydrogen implementation.

Applications Equipments Temperature [°C] Fuels Hydrogen Barriers 5

Low radiation, unknown
effects of the different
Glass Melting ovens 1400–1600 Natural gas, oil, LPG
combustion products
emission
Higher H2 O content in
Lime Rotary kilns 1450–2000 Coal gas, H2 -rich syngas
combustion products
No barriers, for both raw
Ovens for heating and Natural gas, coal gas,
Steel 800–1400 material and combustion
thermal treatments syngas, LPG
emissions
Natural gas, LPG, diesel, Higher H2 O content in
Ceramic Roller kilns 1250–1800
kerosene combustion products
Volumes higher than 10%
Hot water, steam, drying Boilers 1200–1400 Natural gas
for a certain power

5. Conclusions and Future Directions

Hydrogen introduces a remarkable potential for a substantial reduction in CO2 emis-
sions. Numerous technologies are currently in existence or in development, poised to
facilitate the integration of hydrogen into the future energy landscape. While these tech-
nologies hold great promise, the primary hurdles lie in achieving the necessary scale
and ensuring the economic viability and genuine environmental friendliness of hydrogen
generation, distribution, and utilization.
In the present day, and it is presumed at least until 2030, the primary challenges
in adopting hydrogen technology will not be technological but rather centered around
hydrogen availability and cost. Currently, approximately 70 million tons of hydrogen are
produced globally each year, with 99% of this production originating from coal and natural
gas sources. However, if all hydrogen production were to transition to water electrolysis,
it would require an estimated 3600 terawatt–hours (TWh) of electrical energy per year,
which is more than the entire annual electricity production of the entire European Union, as
noted by the International Energy Agency (IEA) in 2019 [117]. Availability issues become
even more challenging if the electricity for water electrolysis is sourced from excess energy
generated by variable renewable energy sources (VRESs). To put this into perspective, the
amount of wind power generation curtailed in Germany in 2016 was 4722 gigawatt–hours
(GWh), whereas the energy required to produce hydrogen through electrolysis to power
just one General Electric 9HA.02 gas turbine for 8000 h at nominal power is 19,600 GWh,
as outlined in the study by Goldmeer [85]. Therefore, even without considering the cost
aspect, from this standpoint, the authors believe that the use of blue hydrogen, produced
from fossil fuels with carbon capture and storage, will be essential to establish a practical
hydrogen value chain. This approach can pave the way for the broader utilization of
green hydrogen, produced through renewable energy sources, once it becomes available in
sufficient quantities to effectively reduce carbon dioxide emissions.
In the power sector, gas turbines will persist as a crucial component within the global
energy framework, as they complement renewable energy sources and possess a significant
existing installed base. Gas turbines are called upon to serve as a backup (seasonal and
peak), supporting variable renewable energy sources and maintaining the stability of the
electric grid, including voltage and frequency control. This contribution to electric system
flexibility is expected to be significant, even in a projection for the year 2040, as illustrated
in Figure 15, which estimates that the annual operating hours will be less than 3000. In this
context, post-combustion carbon capture technologies are deemed impractical, both from a
technical and economic perspective, as indicated in a report by AECOM in 2020 [118]. It is
Energies 2023, 16, 7174 25 of 29

worth noting that the potential annual reduction in carbon dioxide emissions is achievable
with 100% hydrogen gas turbines exceeding 450 million tons in this scenario.

Figure 15. Capacity of the European electricity system under existing policies and sources of flexibility
with stated policies in the projected 2040 scenario by the IEA [119].

Despite the long history of gas turbines and their diverse applications across various
sectors, ongoing research and development efforts are necessary to ensure their reliable and
safe operation with a higher hydrogen content. The aim is to reach a hydrogen content of at
least 80% by volume, which can lead to a substantial reduction in CO2 emissions. Original
equipment manufacturers (OEMs) are dedicating substantial resources to incorporating
hydrogen-burning technologies into their new engines and crafting modification packages
for existing engines.
In the hard-to-abate sector, the reduction in pollutant emission is even more challeng-
ing. Electrification cannot be implemented in most industrial processes and hydrogen
combustion cannot also be adopted in a straightforward way. In fact, substituting fuel
blends with a high H2 content for natural gas produces changes in the radiative energy
emission and in exhaust gases composition that can have important effects on the industrial
process and the quality of the products. Hence, some research is still needed and more
importantly, communication between industries and research should be enhanced, espe-
cially in the glass and ceramic sectors. The application of hydrogen in furnaces for the steel
industry is instead at an advanced stage.
Beyond the technological challenges that must be overcome, the most significant
barrier to the widespread adoption of hydrogen is its availability, primarily due to its
production cost. Once hydrogen is embraced as a key element in addressing climate change,
the transition to a “hydrogen society” can only be realized by establishing the necessary
infrastructure. In the authors’ view, this transition should begin with the utilization of
cost-effective “blue hydrogen” in the short term, followed by the integration of the more
expensive “green hydrogen” in the long term.

Author Contributions: Structure, writing, E.G., G.T., A.D.N., G.C., D.C., G.M., and S.C.; sources, all;
review, all. All authors have read and agreed to the published version of the manuscript.
Funding: This review study was performed within the Italian project “RICERCA E SVILUPPO
DI TECNOLOGIE PER LA FILIERA DELL’IDROGENO POR-H2” (“Research and Development
of Technologies for Hydrogen Chain”, POR-H2, WP2, LA2.2.5), funded by the Italian Ministry of
Environment and Energy Security, under the National Recovery and Resilience Plan (PNRR, Mission
2, Component 2, Investment 3.5, project code I83C22001170006).
Data Availability Statement: Data related to pictures where ENEA’s articles or technical reports are
cited can be directly asked to the corresponding author.
Conflicts of Interest: The authors declare no conflicts of interest.

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