Progress in Energy and Combustion Science 90 (2022) 100995

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Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Synthesis gas as a fuel for internal combustion engines in transportation

Amin Paykani a *, Hamed Chehrmonavari a, Athanasios Tsolakis b, Terry Alger c,
William F. Northrop d, Rolf D. Reitz e
a
School of Physics, Engineering and Computer Science, University of Hertfordshire, Hatfield, AL10 9AB, UK
b
Department of Mechanical Engineering, School of Engineering, University of Birmingham, Birmingham B15 2TT, UK
c
Automotive Propulsion Systems, Powertrain Engineering Division, Southwest Research Institute, TX, USA
d
Department of Mechanical Engineering, University of Minnesota, 111 Church St. SE Minneapolis, MN, 55419, USA
e
Engine Research Center, University of Wisconsin-Madison, 1500 Engineering Drive, Madison, WI 53705, USA

A R T I C L E I N F O A B S T R A C T

Keywords: The adverse environmental impact of fossil fuel combustion in engines has motivated research towards using
IC engine alternative low-carbon fuels. In recent years, there has been an increased interest in studying the combustion of
Syngas fuel mixtures consisting mainly of hydrogen and carbon monoxide, referred to as syngas, which can be
Fuel reforming
considered as a promising fuel toward cleaner combustion technologies for power generation. This paper pro-
Combustion
Efficiency
vides an extensive review of syngas production and application in internal combustion (IC) engines as the pri-
Emissions mary or secondary fuel. First, a brief overview of syngas as a fuel is presented, introducing the various methods
for its production, focusing on its historical use and summarizing the merits and drawbacks of using syngas as a
fuel. Then its physicochemical properties relevant to IC engines are reviewed, highlighting studies on the
fundamental combustion characteristics, such as ignition delay time and laminar and turbulent flame speeds. The
main body of the paper is devoted to reviewing the effect of syngas utilization on performance and emissions
characteristics of spark ignition (SI), compression ignition (CI), homogeneous charge compression ignition
(HCCI), and advanced dual-fuel engines such as reactivity-controlled compression ignition (RCCI) engines.
Finally, various on-board fuel reforming techniques for syngas production and use in vehicles are reviewed as a
potential route towards further increases in efficiency and decreases in emissions of IC engines. These are then
related to the research reported on the behavior of syngas and its blends in IC engines. It was found that the
selection of the syngas production method, choice of the base fuel for reforming, its physicochemical properties,
combustion strategy, and engine combustion system and operating conditions play critical roles in dictating the
potential advantages of syngas use in IC engines. The discussion of the present review paper provides valuable
insights for future research on syngas as a possible fuel for IC engines for transport.

minimize greenhouse gas (GHG) emissions on a well-to-wheel basis to

meet worldwide emissions legislation [4]. The next generation of
1. Introduction cleaner fuels is governed by several important factors, including the
availability of the feedstock, production efficiency and environmental
Worldwide, approximately 80% of useful energy, including high- impact, distribution and storage, safety issues, integration and
quality heat, propulsion work, and electricity, is produced by compatibility with engines, vehicle, and transportation systems – costs,
combustion-driven processes using fossil fuels. The main detriments of regional variations, standardization and public acceptance [5,6]. In this
the application of fossil fuels in IC engines are their contribution to regard, natural gas [7,8], hydrogen [9] and ammonia [10,11] and
global warming and environmental pollution, and therefore govern- optimized engines [12] have recently drawn much attention from en-
ments are encouraging the use of zero/low-carbon fuels in power and gine researchers to meet the future emission standards.
propulsion systems for achieving energy security and meeting emissions Hydrogen (H2) has been considered as a viable energy carrier for fuel
targets [1,2]. In the coming decades, both IC engine efficiency and fuel cells and future IC engines. The wide flammability range of hydrogen
technology must improve and contribute to achieving carbon-neutral makes it suitable for engine operation over a wide range of air-fuel
transportation [3]. Engine technology must also use fuels that

* Corresponding author:
E-mail address: a.paykani@herts.ac.uk (A. Paykani).

https://doi.org/10.1016/j.pecs.2022.100995
Received 30 June 2020; Received in revised form 3 February 2022; Accepted 6 February 2022
Available online 18 February 2022
0360-1285/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

Nomenclature HRR Heat release rate

HTHR High-temperature heat release
Greek HWFET Highway Fuel Economy Test
λ Air–fuel equivalence ratio ICE Internal combustion engine
ϕ Fuel–air equivalence ratio IDT Ignition delay time
γ Ratio of specific heats IGCC Integrated gasification combined cycle
θ Crankshaft angle IMEP Indicated mean effective pressure
η Efficiency ITE Indicated thermal efficiency
LFS Laminar flame speed
Abbreviations LD Light duty
AFR Air fuel ratio LFG Landfill gas
AHRR Apparent heat release rate LHV Lower heating value
AKI Anti-knock index LPG Liquefied petroleum gas
ATDC After top dead center MAP Manifold absolute pressure
ATR Autothermal reforming MBT Maximum brake torque
BMEP Brake mean effective pressure MES Methane enriched syngas
BSFC Brake specific fuel consumption MFB Mass fraction burned
BTDC Before top dead center ML Machine learning
BTE Brake thermal efficiency MN Methane number
CA Crank angle NIMEP Net indicated mean effective pressure
CDC Conventional diesel combustion NOx Nitrogen oxides
CFD Computational fluid dynamics NTC Negative temperature coefficient
CFR Cooperative fuel research NVO Negative valve overlap
CHP Combined heat and power PG Producer gas
CI Compression ignition POX Partial oxidation
CN Cetane number PPM Parts per million
CNG Compressed natural gas PRF Primary reference fuel
CO Carbon monoxide PRIEMER Premixed mixture ignition in the end-gas region
COV Coefficient of variation RCCI Reactivity controlled compression ignition
CR Compression ratio R-EGR Reformed exhaust gas recirculation
CRI Common rail injector RG Reformer gas
D-EGR Dedicated exhaust gas recirculation RMG Reformed methanol gas
DFBG Dual fluidized bed gasifier RON Research octane number
DF Dual fuel SAC Superadiabatic combustion
DI Direct-injection SAE Society of Automotive Engineers
DISI Direct injection spark ignition SEC Specific energy consumption
DME Dimethyl ether SI Spark ignition
DNS Direct numerical simulation SMR Steam methane reforming
EGR Exhaust gas recirculation SOC Start of combustion
EPA Environmental protection agency Syngas Synthesis gas
ERC Engine research center SZM Single zone model
FTP Federal test procedure SwRI Southwest Research Institute
FT Fischer –Tropsch TCR Thermochemical recuperation
GA Genetic algorithm TFR Thermochemical fuel reforming
GDI Gasoline direct injector TFS Turbulent flame speed
GHG Greenhouse gas emissions THC Total hydrocarbons
GIE Gross indicated efficiency TIDR Total inert dilution ratio
GT Gas turbine TWC Three-way catalyst
GTL Gas-to-liquid UHC Unburned hydrocarbons
HCCI Homogenous charge compression ignition WGS Water–gas shift
HD Heavy-duty WHR Waste heat recovery
HE Hydrous ethanol WOT Wide-open throttle
HOME Honge oil and its methyl ester

mixtures, and the lean mixture operation can increase the fuel economy In contrast, hydrogen’s high auto-ignition temperature (858 K) ne-
of the hydrogen-fueled engines. Moreover, its high diffusivity and flame cessitates the use of a spark plug or a supplementary low auto-ignition
speed result in a faster uniform fuel/air mixture and an improved temperature fuel. On the other hand, its low ignition energy increases
combustion inside the cylinder [13,14]. The carbon-free structure of the the propensity of phenomena like pre-ignition, backfire and knock. NOx
hydrogen also makes it an excellent fuel for the clean and efficient emissions can also be increased due to the higher combustion temper-
operation of IC engines. Fig. 1 shows the energy density of various fuels atures associated with hydrogen combustion in IC engines [15].
based on lower heating values (LHV) compared to hydrogen. As can be Hydrogen can be produced in various ways to be stored in a pres-
seen, hydrogen has nearly three times the energy content of gasoline on surized tank on-board in a vehicle aiming at improving both combustion
a mass basis. and aftertreatment processes [17]. The comparison of hydrogen usage in

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

stored liquid fuels on vehicles can mitigate many of the hydrogen stor-
age and combustion challenges [27–31], and this will be extensively
discussed in the upcoming sections.

1.1. What is syngas?

Syngas (an abbreviation for synthesis gas) can be derived by gasifi-

cation processes from natural gas, heavy oil, biomass, and coal (carbon-
containing fuels) for stationary application or by chemical processes
from liquid and gaseous fuels for vehicular application, in which a
complex and long-chain molecule converts to simpler molecules
including H2 (hydrogen), CO (carbon monoxide), and CH4 (methane),
CO2 (carbon dioxide), H2O (water vapor), and N2 (nitrogen). Based on
the process adopted and the type of feedstock used, end-products as a
form of syngas will have varying compositions and heating values, thus
different terms such as “town gas”, “wood gas”, “water gas”, “producer
gas”, “reformer gas”, “power gas”, and etc. have been used in the litera-
ture. A possible range for the volumetric composition of syngas is shown
in Table 2, indicating that it is comprised mainly of H2 and CO. The
preferred composition generally depends upon the purpose of syngas
usage, feedstock, and production cost. For example, if the goal is
hydrogen production by a biomass gasification process, much more cost
and effort are needed for adequate purification than the reaction
Fig. 1. Gravimetric and volumetric density of hydrogen and other fuels [16]. reforming process.
Syngas can also be produced through fuel reforming with steam and/
vehicles through on-board hydrogen production, hydrogen storage, and or air using compact systems that can be located on-board a vehicle [27,
stationary power generation systems is summarized in Table 1. The low 33,34]. External on-board and in-cylinder fuel reforming techniques
ignition energy and volumetric energy density make storage of hydrogen have been identified as possible pathways to produce syngas on-board in
on-board a challenging task [18,19]. Hydrogen as a low-density fuel IC engines to improve efficiency and emissions [33]. The details of
needs to be compressed at high-pressure tanks (350–700 bar) to allow an on-board fuel reforming and syngas production will be covered in sec-
adequate driving range of more than 500 km with safety and cost to be tion 4.
the main challenging issues. Difficulties involved in the storage and
transport of hydrogen still present barriers to the commercial use of 1.2. Syngas applications
hydrogen as a secondary or a main fuel for IC engines [19,20]. However,
hydrogen is currently viewed as the most promising clean energy carrier Syngas can be used as an intermediate to create other attractive clean
of the future, and the hydrogen infrastructure is now rapidly expanding fuels such as ammonia (NH3), dimethyl ether (DME), and methanol
in many counties, both in the EU and outside. This has sparked research (CH3OH) [35–39]. Another use of syngas is as a primary chemical
interest in the energy conversion technologies, particularly fuel cells building block in petrochemical and refining processes [40]. Syngas can
that are capable of using hydrogen as the fuel [21]. be used in many different applications, including:
While the merits of operating IC engines with varying concentrations
of hydrogen have been well documented [25], the key challenges • Power generation in existing coal power plants [22]
remain unresolved, including practical approaches to hydrogen pro- • Combined heat and power (CHP) plants [41]
duction without sacrificing system efficiency and/or sufficiently • Integrated gasification combined cycles (IGCC) [42]
addressing its adverse combustion properties [26]. Syngas is considered • Fuel cells [43–46]
an intermediate step in the transition from carbon-based fuels to • Production of transportation fuels from gas-to-liquid (GTL) processes
H2-based fuels, since it is composed mainly of hydrogen (H2) and carbon [47]
monoxide (CO). In IC engines, using syngas produced from on-board • Gas turbines [48–50]
• Directly as the primary or secondary fuel in IC engines [51]

Table 1
Comparison of hydrogen usage in vehicles through on-board hydrogen pro-
duction, hydrogen storage, and stationary power generation systems [22–24].
Transportation (on-board Transportation Stationary power
in vehicles) (storage in vehicles) generation Table 2
A possible range for syngas composition on a volume percent basis [29,32].
• Ability to operate on H2 • Ability to operate on • Ability to operate on
partly 100% H2 100% H2 Species Min Max
• More complicated design • Simple design • Simple design
• Less space required • More space required • No space problem H2 8.6 61.9
• Few safety concerns • Serious safety • No safety problem CO 22.3 55.4
• Challenge with the catalyst concerns • Hydrogen can be CH4 0.0 8.2
activation under a wide • Challenge with produced or can be CO2 1.6 30.0
range of temperature and hydrogen production, used from the N2+Ar 0.2 49.3
reactants changes store and distribution storage system H2O - 39.8
• Moderate cost • Highest cost • Lowest cost H2/CO 0.33 2.36*
• Fast response during • Fast response during • Aesthetic issues are LHV (MJ/m3) 5.02 12.57
transient operation is a transient operation not important *
The broad experimental studies of syngas-fed IC engines reviewed in sec-
challenge
tions 3 and 4 have been performed with simulated syngas whose H2/CO ratio
• Aesthetic issues
can go beyond this value, i.e., H2/CO: 3/1 (by vol.).

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

1.3. Syngas production methods power generation. The biomass used consisted of bones and meat resi-
dues sampled directly from the industrial line, characterized by high
Solid fuel (coal, biomass, wastes) feedstocks are sources for syngas water content, about 42% in mass, and potential health risks. They re-
production [52,53] by traditional gasification methods [54,55]. Also, ported that syngas with a composition of 19.1%CO, 17%H2, and 1.6%
liquid and gaseous feedstocks can be converted to syngas by CH4 was produced.
non-gasification methods [56] that comprise one or a chain of reforming New gasification concepts such as dual fluidized bed gasifiers (DFBG)
processes using the catalysts; such processes are expected to be viable [76], plasma gasification [77–80], and supercritical water gasification
in-situ methods of syngas production for automotive engines. In this [81,82], have demonstrated the potential to improve syngas quality
section, only a brief review of different syngas production methods is from biomass gasification. However, they are not of significant interest
presented since several comprehensive review papers [57,58] explain at present, and are more applicable for stationary power generation.
them in detail and emphasize the IC engine operation with gasification Moreover, wood and solid fuels seem to be not effective for transport
fuel [59,60] and non-gasification fuel [33]. applications due to their low energy density. A further analysis on this
topic is presented in section 3.
1.3.1. Gasification processes
Biomass gasification converts a solid fuel into syngas which can be 1.3.2. Non-gasification processes
burnt in stationary gas turbines and IC engines. Gasification is a ther- Non-gasification processes include catalytic fuel reforming, where
mochemical process that converts a solid hydrocarbon feedstock like the parent fuel reacts with steam and/or oxygen in a heterogeneous
coal, petroleum coke, refinery residuals, biomass, and municipal solid process to produce syngas [27,83]; and non-catalytic processes like
waste, into syngas without consuming a large part of its heating value plasma-assisted reforming [84]. The three main global reactions in fuel
[58]. In gasification, the carbon-containing feedstock reacts with a reforming are partial oxidation (POX), steam reforming (SR), and
gasifying agent like oxygen, steam, and air, which breaks down the auto-thermal reforming (ATR) [47,85], which will be explained in the
mixture into syngas, as illustrated in Fig. 2 [54,57,61,62]. The type and following.
design of the gasifier, gasification temperature, type and flow rates of When a mixture of sub-stoichiometric oxygen and feedstock reacts to
the feedstock and oxidizing agents, and type and amount of catalysts produce syngas, this self-sustaining chemical reaction is called “partial
[63], are the main parameters in influencing the gasification process and oxidation (POX),” It is an exothermic reaction. The complete combustion
syngas production [64–70]. Oxygen as the gasifying agent produces reaction forming CO2 is restricted due to insufficient O2 in the reactants
syngas called “medium syngas,” and if air is used, then it is called “pro- [86,87]. In endothermic steam reforming (SR), a high-temperature
ducer gas” [71]; the following sub-section will clarify the terms used in mixture of fuel and steam is sent through a bed of catalyst. The heat
the rest of the paper. Using gasification methods, in addition to H2 and required to drive the endothermic reaction is provided externally (e.g.,
CO, other typical products including H2O, CO, CH4, unwanted tars, electric heaters or combustion of fuel). The syngas stream from the
small amounts of NH3, and H2S are also produced. The relative amount steam reforming can then flow to a water gas shift (WGS) reactor, where
of each species depends on the feedstock and the gasification process additional steam converts CO to CO2 and generates additional H2
[57]. Modeling approaches for biomass gasification have been exten- [88–91].
sively reviewed in [72]. When both the POX and SR reforming reactions are combined in a
For syngas production, a typical solid fuel gasification system single reactor, it is called autothermal reforming (ATR). Industrially, the
coupled to spark ignition and dual-fuel diesel engines is illustrated in ATR reactor is implemented in a refractory-lined pressure vessel with a
Fig. 3 [73]. The system includes a gasifier, a gas clean-up and cooling combustion chamber, burner, and catalyst bed. In this reactor, a sub-
system, a gas mixer, a starting blower, and the engine. The engine draws stoichiometric environment oxidizes fuel, natural gas in most cases,
air from the gasifier during the intake stroke, through the cleaning with O2. In the ATR reaction, POX provides heat for later SR reactions,
system, and from the gas mixer where air is combined with the syngas thus controlling the exit temperature of the reactor. Endothermic dry
[74]. For example, Marculescu et al. [80] used food processing industry reforming (DR) where the CO2 is reacting with hydrocarbons feedstock
waste for energy conversion, using gasification and an IC engine for to create H2 and CO can also be employed [92–95]. The advantages and

Fig. 2. Schematics of biomass gasification process [66].

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

Fig. 3. a) Syngas production system for an SI engine (Reprinted from [73] with permission of Elsevier); b) diagram of the entrained-flow gasifier for power gen-
eration on dual-fuel diesel engine (Reprinted from [75] with permission of Elsevier).

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

disadvantages of these processes and the corresponding chemical re- 1956 by Szezich [108]. Later, further interest in biomass-based fuel
actions are summarized in Table 3 as main reforming reactions and in application in engines was sparked by the oil crisis in the mid-1970s
Table 4 as side reactions that may occur. These fuel reforming processes [109]. Simultaneously, in response to the oil price shocks, US
have been proposed for on-board hydrogen-rich gas production in Congress passed the first national standards for tailpipe-out emissions to
vehicular applications, discussed in detail in section 4. Note that the goal increase miles per gallon (mpg) of passenger vehicles within ten years
is high hydrogen content; therefore, understanding the nature of these [110], which was the onset of adopting further stringent regulations for
reactions aids us in deciding which reactions should participate in oil-based fuels. As already mentioned, by that time, syngas use was
reforming processes within a designed reactor and which ones to avoid. mainly limited to IGCC for stationary power generation [40,111,112],
and as an intermediate to produce other biofuels [113,114].
1.3.3. Syngas as an IC engine fuel On the other hand, fuel reforming has been used for producing
Syngas as an IC engine fuel can be utilized in power generation and syngas industrially for more than 70 years [115], but the concept of
transportation, produced mainly by gasification and reforming pro- compact on-board reforming for engine applications dates back to the
cesses, respectively. As mentioned above, syngas names would be 1970s [116]. Investigations carried out in 1973–1975 in the US with a
different based on composition and LHV, while the terminology we use Chevrolet car with an engine equipped with a syngas generator
throughout the current work can be seen in Fig. 4, taken from IC engine- demonstrated a decrease in petrol consumption by 26% when driving
relevant published works. It is worth noting that the figure does not according to the Federal Drive Cycle CVS-3 [117]. On-board fuel
encompass all viable routes for syngas production. reforming was first practically applied to a carbureted gasoline engine
As seen in the first row of Fig. 4, producer gas (PG) or low heating through a project named “Boston Reformed Fuel Car” by Newkirk and
value (LHV) fuel [59] is a gasification product with low LHV due to Abel [118], which had an on-board non-catalytic system operated at
using air as the gasifying agent and, therefore, the presence of high N2 higher than T = 1100 ◦ C for the steam reforming reactions of gasoline.
content in products. With steam or oxygen or a combination of both Martin [119] at the University of Arizona demonstrated a better concept
utilized as the gasifying agent, the gasification product can be upgraded of this project using a catalyst to reduce the temperature of the steam
to fuel with a medium LHV. In general, the gasification process suffers reforming of gasoline to around T = 620 ◦ C. In the meantime, Houseman
from low thermal efficiencies (~ < 50%) due to the extra step of and Cerini [120] from the Jet Propulsion Laboratory (JPL) evaluated
vaporizing the moisture contained in biomass and then from tar in the on-board hydrogen generation by adding partial oxidation reforming to
products [101]. Noting that in addition to gas constituents, tar and steam reforming along with the catalyst to perform the whole reforming
residue co-exist in the end-product of gasification, but their amounts process for both hydrocarbon and alcohol feedstocks fueled SI engine. A
reduce as high-temperature steam reforming is employed, as seen in series of works from Lindström and Sjöström [121–123] at the Royal
Fig. 5. Thus, gasification fuel presumably creates concerns of NOx Institute of Technology (Sweden) was seemingly the first investigation
emissions (due to probably high N2 content) and deposit formation in on directly using the recirculated exhaust gases as the primary heat
the combustion chamber, which should be considered when this fuel is supplier for driving the endothermic reactions of the steam reforming
being used as an IC engine fuel. Several IC engine related studies, process and as species that can participate in the reforming process. At
particularly with SI engines, with gasification fuels have been investi- the University of Birmingham, Jones [124,125] evaluated the feasibility
gated so far, which will be discussed in section 3. of this concept as exhaust-gas reforming in more detail by incorporating
In the second row of Fig. 5, reformate or reformer gas (RG) is a the exhaust gases and using the entire fuel feedstock in the reforming
reforming reaction product, which often has high H2 and CO contents process. For more reading on this topic, there are two notable reviews in
with negligible N2 and high heating value. RG can be economically the literature [126,127], and additional discussions are provided in
produced with in-situ methods, which will be discussed partially in section 4.
section 3 (sub-sections of 3.2.2, and 3.3) and comprehensively in sec- The development of syngas-fueled IC engines was not commercial-
tion 4 (on-board fuel reforming technologies). ized because of the low lifespan of the catalysts and tightening of NOx
The overall purpose of using syngas as a primary or secondary IC emission standards. However, research on syngas as a potential fuel for
engine fuel is to benefit from renewable energy sources and clean power IC engines in transportation has gained much interest in recent decades
conversion technologies without scarifying efficiency, power derating, with advances in catalysts and the potential for on-board generation
and pollutant emission formation of engines fueled with syngas [102, through waste heat recovery (WHR). An average of 30% substitution of
103]. However, its advantages are dependent on the physicochemical fossil fuels by syngas has been proposed, based on extrapolating from the
properties of syngas (i.e., the amount of CO and H2) (see section 2), the current EU Directives [128,129]. For further information, several review
type of combustion engine (see section 3), and the fuel reforming papers [27,51,59] and a book chapter [29] have been published on the
technique used for on-board syngas production (see section 4). historical and trends of syngas for power generation.

1.4. Historical use of syngas as an engine fuel

1.5. Scope and structure of the current review
The first application of syngas in vehicles was reported in the 1920s
when German engineer Georges Imbert developed a wood gas generator There are many studies in the literature on the use of syngas in
for automobile use [104]. The gases were cleaned and dried, and then different types of IC engines, and it has been shown that syngas can be
fed into the vehicle’s combustion engine. Later, during World War II, used as a renewable and alternative low-carbon fuel for both spark
shortages of petroleum fuels led to further development of wood gas ignition (SI) and compression ignition (CI) engines [130–133]. How-
vehicles [105,106]. By 1945 syngas was used for trucks, buses, agri- ever, there are still numerous subjects such as on-board syngas pro-
culture, energy generation, and industrial machinery. After the end of duction and application in advanced combustion strategies that require
World War II, the application of syngas was changed to integrated further investigation and review. This work is focused on determining
gasification combined cycles (IGCC) for stationary power generation. syngas’ potential as a renewable IC engine fuel in transportation. To do
This could be due to less interest in syngas usage in IC engines related to this:
the sharp drop in global oil price and intensified ambitions towards high
power engines by increasing the anti-knock index (AKI) of gasoline fuel. • Section 2 presents the fundamental physicochemical characteristics
The 1950s and 1960s are recalled as the “Power Wars” age [107]. The of syngas, which ultimately help us perceive the combustion
potential of syngas production and application in a low compression behavior of syngas as an IC engine fuel under engine-relevant con-
ratio SI engine fueled with a syngas-methane mixture was studied in ditions. Due to the composition variability of syngas, various H2/CO

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Table 3
Advantages and disadvantages of the three main fuel reforming technologies [43,96-98].
Reforming Chemical formulaEnthalpy of Characteristics Advantages Disadvantage
process reaction (kJ mole−1) 1

Steam y Endothermic • Highest H2 generation (H2/CO ~ Highly endothermic

Cx Hy + xH2 O→xCO + x + H2 •
Reforming 2 3:1 by vol.) • Low rate of hydrogen production
(SR) ΔhR = +12591 • Need significant quantity of water
• Complex system regarding working in high
temperature
• Careful thermal management (S/C ratio
control)
• Less fuel flexibility (only certain fuel)
Partial x y Exothermic • Simple system (absence of external Lowest H2 generation
Cx Hy + O2 →xCO + H2 •
Oxidation 2 2 heat and water) and compactness • Lower heating value of reformate than base fuel
1
Reforming ΔhR = −676 • Rapid start • Catalyst’s deactivation issues by Sulphur and
(POX) • Fast response to temperature and coke depositions
reactant changes • Non-catalytic partial oxidation needs costly
• Not have thermal management materials because it operates at very high
issue temperatures
• High fuel-type flexibility
Autothermal z Combination of exothermic • Simple System (lack of water and • H2 and CO selectivity is small, because the
Cx Hy + zH2 O + x− O2 →
Reforming 2 and endothermic external heat requirements) device uses two different catalyst types
y
(ATR) xCO2 + z + H2 (thermally neutral) • Compact • During load changes and start-up, careful con-
2
• Quick to start trol system is required to balance SR and POX
1
With assuming that fuel is n-octane, and reactants and products are both at 273.15 K and 1 bar.

Table 4
Other side reforming reactions that may take place [99,100].
Reforming process Reaction Enthalpy of reaction(kJ mole−1) Notes

Dry reforming y ΔhR = +15881 Lower H2 yield than SR (H2/CO ~ 1:1 by vol.).
Cx Hy + xCO2 →2xCO + H2
(DR) 2 Likely to happen at high temperature and low pressure.

Combustion y y ΔhR = −51161 If enough O2 is available.

Cx Hy + x + O2 →xCO2 + H2 O
(complete oxidation) 4 2

Water-gas shift (WGS) CO + H2 O

↼
CO2 + H2 ΔhR = −411 A route to CO purification and thus increased H2 yield at low temperatures.
⇁
Methanation 1 ↼
CO + 3H2 CH4 + H2 O ΔhR = −2061 H2 will be consumed to increase CH4 yield.
⇁
1
Methanation 2 ↼
CO2 + 4H2 CH4 + 2H2 O ΔhR = −165
⇁
Boudouard ↼
2CO2 CO2 + C ΔhR = −1721 Undesired reaction in catalytic reforming
⇁
Thermal Decomposition C8H18 → CH4 + C7H14 Endothermic May occur on the catalyst and increase CH4 yield.

Hydrogenolysis C8H18 + H2 → CH4 + C7H16 Exothermic May occur on the catalyst and increase CH4 yield.
1
Assuming that the fuel is n-octane, and reactants and products are both at 273.15 K and 1 bar.

Fig. 4. Syngas terminology used in the current review paper.

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

• The transition from syngas as an IC engine fuel to syngas as a

transportation fuel requires producing and carrying the syngas on-
board a vehicle, such that both fuel economy and engine efficiency
can increase. We discuss all proposed on-board fuel reforming
technologies compatible with IC engine in section 4 to achieve these
goals, especially paying attention to waste heat recovery (WHR)
from engine exhaust.
• The final section represents the summary and demonstrates sugges-
tions to make a feasible future for syngas as a transportation fuel.

2. Fundamentals

2.1. Physicochemical properties of syngas relevant to engines

Table 5 lists the physicochemical properties of typical syngas mix-

tures compared to hydrogen, methane, biogas, and conventional fossil
fuels. It is apparent that syngas has the highest laminar flame speed and
widest flammability limits amongst all fuels after hydrogen, making it
beneficial for application as a secondary fuel in IC engines, especially at
low engine loads. It means that a wide range of stable operation (from
rich to lean) could be achieved with syngas fuel, especially promoting
the ultra-lean combustion in spark-ignition engines. The volumetric
energy content is the main parameter determining the fuel injection
system design and required storage tank for vehicular applications
[134]. In the case of syngas use in IC engines, the fuel injection system
size should be larger, or the injection duration should be longer.
Although there is no available data for the minimum ignition energy
of syngas mixtures, it can be concluded that the high hydrogen content
in syngas could facilitate cold starts and guarantee rapid ignition [135],
considering the unwanted ignitions, specifically pre-ignition and back-
fire (see sub-section 3.1.1). A scarcity in data has also continued for the
Fig. 5. Yield of product for biomass gasification with thermal decomposition
and steam reforming (Reprinted from [101] with permissions of Elsevier). quenching distance, and a lower value means a more complete com-
bustion [136], but with a higher heat transfer losses.
Detailed combustion characteristics of syngas mixtures for gas tur-
mixtures are considered in the first place, then the effects of diluents
bine engine-relevant conditions have already been reviewed by Lee et al.
are discussed.
[137] and Jithin et al. [138]. In the following section, characteristics of
• To better understand the effects of syngas on combustion, emissions,
the ignition delay times, laminar and turbulent flame speeds of syngas
and performance of IC engines with conventional and advanced
mixtures under engine-relevant conditions are reviewed and discussed
combustion strategies, section 3 reviews the syngas application in SI,
with a focus on those aspects which have not been addressed carefully in
HCCI and dual-fuel engines. In SI engine section, the power gener-
previous reviews.
ation applications of the syngas-fueled engines are also included.

Table 5
Physicochemical properties of a typical syngas mixtures compared to other fuels [59,139-143].
Properties Syn11 Syn21* Syn31 Syn41þ Syn51þ Biogas Hydrogen Carbon Methane Gasoline Diesel
* monoxide

Density [kg/m 3] 2 0.54 0.67 0.68 1.05 1.04 1.11 0.0824 1.145 0.656 719.7 832
Molecular weight [kg/kmol] 2 13.91 15 15.2 23.2 34.4 2.0 28 16.04 103 200
Stoichiometric air/fuel ratio [kg/ 5.3 4.58 7.23 1.4 2.07 5.67 34.2 2.5 17.2 14.7 14.7
kg]
Flammability limits [vol.% in air] 24-60 6.06- 5.8- 7-21.6 13.4-58 7.5-14 4-75 12.5-74 5-15 1.4-7.6 0.6-
74.2 41.4 7.5
Flammability limit [ϕ] 0.2-7.2 - - - - - 0.1-7.5 0.3-6.8 0.4-1.6 0.7-4.3 1.0-
6.5
Autoignition temperature [K] 980 873-923 873- 898 898 923 858 882 813 550 589
923
3
Minimum ignition energy [mJ] - - - - - - 0.02 - 0.28 0.24 -
Laminar flame speed [m/s] 3 1.0 1.8 - 0.5 0.5 0.25 1.8-2.8 0.4 0.38 0.37- -
0.43
Adiabatic flame temperature [K] 3 2584 2385 2400 - 2200 2145 2390 2214 2214 2580 -
Quenching distance [mm] 3 - - - - - - 0.64 1.6 2.1 2.84 -
Lower heating value [MJ/kg] 15.7 17.54 24.4 5 7.47 17.0 119.7 10.1 50.0 43.4 42.6
Volumetric energy content [MJ/ 8.47 11.75 16.59 5.25 7.84 18.87 9.86 11.56 32.8 31235 35443
m3]
1
Syn1:57/43:H2/CO, Syn2:50/50:H2/CO, Syn3:40/40/20:H2/CO/CH4, Syn4: 22.6/24.3/2.2/9.3/41.2:H2/CO/CH4/CO2/N2, Syn5: 19.6/29.6/5.27/5.41/40.56:
H2/CO/ CH4/CO2/N2 and Biogas: 55.6/42.3/2.1: CH4/CO2/N2 (by volume).
2
at NTP: normal temperature (T=298.15 K) and pressure (p=1 bar). 3 at ϕ=1 (stoichiometry).
*
A typical reformate, + A typical producer gas

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

+ OH reaction. Those works were completely reviewed in [157,158].

Recently, in order to justify the observed discrepancies, Mansfield
and Wooldridge [159] indicated two distinct ignition behaviors attrib-
uted to the strong (or spontaneous ignition which is referred to as
spatially homogeneous ignition) and mild ignition (or deflagration
ignition which is characterized by the onset of localized reaction sites)
for a syngas, with a molar ratio of H2/CO = 0.7, mixed with air (O2/inert
gas molar ratio = 1/3.76) at ϕ = 0.1 and 0.5, T = 870-1150 K, and p =
3-15.4 bar through high-speed imaging in RCM experiments. Two
high-speed imaging frames of that work are depicted in Fig. 7, in which
multiple localized flame-like structures can be seen on the right side. The
authors [159] indicated that the ignition behavior is weakly affected by
the molar ratio of H2/CO, and, by comparison to other work [160], is not
strongly dependent on the combustion device used, albeit strongly
dependent on the initial thermodynamic state (i.e., pressure, tempera-
ture, and equivalence ratio). Also, they stated that the mild ignition
behavior is not avoidable by reducing the equivalence ratio towards lean
condition; however, the available chemical kinetics mechanisms used in
the zero-dimensional (0-D) homogeneous reactor modelling would be
capable of predicting the IDTs quite accurately.
Fig. 6. Discrepancies of ignition delay times between five homogenous reactor As mentioned earlier, a review by Lee [137] evaluated IDTs of syngas
models’ predictions and three experimental datasets for syngas (H2/CO: 50/50, mixtures at different H2:CO ratios with different pressures ranging from
by vol.)/air mixture at ϕ = 0.5 and p = 20.2 bar (Reprinted from [156] with 1.6 to 49 atm, by collecting data from Krejci et al. [161,162], Mathieu
permission of Elsevier). et al. [163], Vasu et al. [164], Keromnes et al. [165], Gersen et al. [166],
and Mittal et al. [152], as shown in Fig. 8. Relying on this review and
2.2. Ignition delay time (IDT) related works, the effects of various parameters on IDTs of syngas
mixtures are summarized below:
The ignition delay times, IDTs, of syngas mixtures were measured in Temperature and equivalence ratio (ϕ) effects:
earlier studies mostly using a shock-tube apparatus confined to low While increasing the temperature shortens the IDT substantially, the
pressure (up to 2.2 bar) and low-to-high temperature (up to 2850 K) IDT of the various compositions of H2/CO syngas at lean equivalence
conditions, which are less applicable to typical gas turbines and IC en- ratios (ϕ) has a decreasing trend, but only at higher pressures, e.g., 49
gines operating conditions [144–150]. The emergence of advanced in- atm, as seen in Fig. 8(h). Conversely, at lower pressures, e.g., 7.9 atm,
tegrated system technologies like syngas-fired IGCC as an alternative to the IDTs can have an increasing trend by reducing the ϕ, which is the
conventional coal-fired power plants, together with reported discrep- case of Fig. 8(b).
ancies between measurements and reaction model predictions of IDTs of Pressure effect:
syngas mixtures (see Fig. 6), has provoked researchers to reproduce The influence of pressure on IDT of 50:50 H2:CO at ϕ = 1.6, and at p
experimental measurements and refine the reaction kinetics for syngas = 8, 12, and 32 atm are shown in Fig. 9 (left). The complex behavior of
oxidation at higher pressures and temperatures [151,152]. Thus, some IDT can be seen with altering pressure at different temperature regions.
later studies were conducted using rapid compression machines (RCM) At high temperatures (>1250 K), higher pressures significantly shorten
[152–154] and shock-tubes [155,156] at higher pressures, suggesting the IDT, while at intermediate temperatures (1110 K<T<1250 K),
that the observed discrepancies between measured and calculated IDTs increasing pressure from 1.6 to 32 atm exhibits a mild decreasing and
at these pressures are due to not considering the overall activation en- even increasing decreasing trend for IDT, which implies that a compe-
ergy correctly, HO2/H2O2 chemistry dominance in the tition effect may exist. Actually, this was attributed to the pressure
chain-propagation regime, and particularly the role of CO + HO2 = CO2 dependence of H2 ignition [165], which is the competition between the

Fig. 7. High-speed imaging of homogenous (left) and inhomogeneous (right) ignition behaviors of syngas, with a molar ratio of H2/CO = 0.7, mixed with air (O2/
inert gas molar ratio of 1/3.76) illustrating uniform and non-uniform chemiluminescence (Reprinted from [159] with permission of Elsevier).

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A. Paykani et al. Progress in Energy and Combustion Science 90 (2022) 100995

Fig. 8. Ignition delay times of different H2:CO mixtures as a function of temperature at different pressures (Reprinted from [137] with permission of Elsevier).

chain branching reaction (H + O2 → O + OH) that dominates in the concentration (i.e., CO < 60%), adding CO to H2 did not lead to a sig-
high-temperature region, and the pressure-dependent propagation re- nificant increase in IDT, as shown by Gersen et al. [166] (see Fig. 8 (a)).
action (H + O2(+M) → HO2(+M)) that dominates in the Further discussions regarding the CO’s inhibiting effect have been re-
low-temperature region. Moreover, the latter reaction is more favorable ported in [152,166].
at high pressures and is also pressure-dependent, inhibiting the chain CH4 effect:
branching and resulting in longer IDT at elevated pressures, as seen in Under engine-relevant conditions, it has been reported [167–169]
Fig. 9 (right). that the addition of H2 has ignition-promoting effect in CH4 mixtures,
CO effect: with substantially reduced IDT by replacing CH4 with a 50% mole
Though the H2-chemistry is dominant at low CO content, the CO has fraction of H2, particularly at higher temperatures. For the purpose of
an inhibiting effect on the IDTs of H2/CO fuel due to the decrease in IDT measurement in CH4/H2/CO/oxidizer mixtures, Gersen et al. [166]
activation energy. Lower activation energy can be detected in the high- carried out experiments and calculations at ϕ = 0.5 and 1, p = 20-80 bar,
temperature region, followed by a very steep increase at around T = and T = 900-1100 K conditions using an RCM and the SENKIN code
1000 K. The inhibition effect is much more prominent as pressure in- [170]. With the addition of CH4 (> 50% by mole fraction) to the
creases from ~15 to 30 bar; that is, the CO oxidation is retarded by H2/CO-oxidizer mixture, CO, with low mole fraction (≤ 30%), had no
increasing pressure. Beyond p=30 bar, the incremental variation in the inhibiting effect on either IDTs of CH4/H2/CO or CH4/CO, while CH4
inhibiting effect would be trivial. These mentioned trends can be seen in had this effect, particularly at high temperatures, as illustrated in Fig. 10
the labeled pictures of (a), (c), (e), and (g) in Fig. 8. For high H2 (a). In contrast to CO, CH4 with an even low mole fraction (~ 6%) in the

10