Renewable and Sustainable Energy Reviews 91 (2018) 394–408

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Overview of the oxygenated fuels in spark ignition engine: Environmental T

and performance
⁎
Omar I. Awada, , R. Mamata, Thamir K. Ibrahimb, Ali Thaeer Hammidc, I.M. Yusria,
Mohd Adnin Hamidia, Ali M. Humadad, A.F. Yusopa
a
Faculty of Mechanical Engineering, Universiti Malaysia Pahang, 26600, Pekan, Pahang
b
Department of Mechanical Engineering, College of Applied Engineering, University of Tikrit, Tikrit, Iraq
c
Al Yarmouk University College, 32001 Ba'aqubah, Diyala, Iraq
d
General Company of Energy Production, Salahadden, Ministry of Electricity, Iraq

A R T I C LE I N FO A B S T R A C T

Keywords: Oxygenated fuels such as alcohols and ethers have the potential to provide reliable sources, and environmentally
Alcohols fuel friendly fuel to world's increasing future energy demands. Oxygenated fuels have a promised future since are
MTBE renewable and produced from several sources, also can be produced locally. The first objective of this paper is to
Spark ignition engine systematically review of oxygenated fuels including alcohol and ether regarding the production, environmental
Engine emissions
impacts and potential using as octane booster of gasoline that used in spark ignition SI) engine. Another ob-
Oxygenated fuel
jective of this paper is to review the effects of oxygenated fuels on performances and emissions characteristics of
spark ignition engine. Alcohol and ether burn very cleanly than regular gasoline and produce lesser carbon
monoxide (CO) and nitrogen oxides (NOx). Mainly the ether fuels (methyl tertiary butyl ether MTBE and
Dimethyl Ether DME) are used as additives at low blending ratio to enhance the octane number and oxygen
content of gasoline. Furthermore, alcohols and ethers have significant impacts on the environment, greenhouse
gas and human health. In addition to this, application of oxygenated fuel on SI engines can decrease environ-
mental pollution, strengthen agricultural economy and decrease gasoline fuel requirements. The increase in
engine performance could be attained with an increased compression ratio along with the use of alcohol fuels
which have a higher-octane value. Overall, oxygenated fuels have been found to be a very promising alternative
fuel for SI engines, capable of providing high thermal efficiency, and lower NOx levels.

1. Introduction valued as a serious environmental matter. Fig. 2 shows the increase of

It is well recognized that transportation sector is almost entirely
dependent on conventional fuels especially petroleum-based fuels such
as gasoline and diesel fuel. Currently, combustion of gasoline and diesel
account for more than half the world's primary energy use [1,2]. With
the increasing cost of fossil oil and global warming continuing to be a
dominant environmental concern, it seems that the use of alternative
fuels in the future is inevitable [3]. TheEnergy Information Adminis-
tration (EIA) reported the increase in the world energy consumption
would be around 56% by 2040 compared with that of the year 2010 as
shown in Fig. 1 Besides that, the increasing utilization of conventional
fuels as major energy carriers and the resultant emissions have been
CO2 emissions by 3.5 times from 1961 to 2010 that published by
Carbon Dioxide Information Analysis Center (CDIAC).
Oxygenated fuels such as alcoholic and ether fuels which have sig-
nificant oxygen content. Oxygenated can be naturally produced from
conventional biomass resources which are environmentally friendly,
are biodegradable and contribute to sustainability. Producing and uti-
lizing oxygenated fuels in an internal combustion engine (ICE) an al-
ternative to conventional fuels that can assist provide solutions to many
environmental problems [6]. Actually, the utilizing of oxygenated fuels
in internal combustion engine lead to reduce greenhouse gas (GHG)
emissions compared to gasoline [7,8]. This could be explained by the
low content of pollutants like sulfur in oxygenates, and to complete

Abbreviations: ICE, Internal combustion engines; RVP, Reid vapor pressure; LUC, Land-use change; GHS, Greenhouse gases; RON, Research octane number; MON, Moto octane number;
TEL, Tetraethyl lead; BTE, brake thermal efficiency; BSFC, brake specific fuel consumption; VEL, various engine loads; VES, various engine speeds; DISI, Direct Injection Spark Ignition;
DME, Dimethyl Ether; DMF, dimethylfuran; MTBE, methyl tertiary butyl ether; IMEP, indicated mean effect pressure; 3 C, three-cylinder; 4 C, four-cylinder; SC, single cylinder; 4 S, four
stroke; CFR, cooperative fuels research; DST, different spark timing; CR, compression ratio; VCRC, variable compression ratio capabilities; LHOV, latent heat of evaporation; BTDC, before
top dead center
⁎
Corresponding author.
E-mail addresses: omaribr78@gmail.com (O.I. Awad), thamirmathcad@yahoo.com (T.K. Ibrahim).

https://doi.org/10.1016/j.rser.2018.03.107
Received 23 April 2017; Received in revised form 15 March 2018; Accepted 31 March 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
O.I. Awad et al.
Fig. 1. The estimated amount of world energy consumption.
Source: EIA (2015) [4]
Fig. 2. The amount of CO2 emission emitted.
Source: Marland, Boden et al., 2007 [5]
combustion.
It is commonly known that fossil fuels are energy sources that are
non-renewable [9,10]. Alcohol-based oxygenated fuels may have been
regarded as one of the renewable solutions, with a potential to be used
in a near CO2 neutral manner through efficient conversion of bio-
mass [11,12]. Alcohols have a long history of approximately 100 years
as fuels in internal combustion engines (ICE). Alcohols such as ethanol,
butanol, methanol, and fusel oil and ethers (MTBE and DME) are used
as fuels in ICE [13,14]. First generation alcohols for spark ignition (SI)
applications have so far largely based on gasoline-ethanol blends,
where current fuel quality standards typically allow between 5% and
10% inclusions of ethanol within an existing gasoline pool.
Methanol was used as vehicle fuel during the 1930s to replace ga-
soline supplies in high-performance engine [15,16]. Butanol or butyl
alcohol is four-carbon atom alcohol (C4H9OH) that can be used in non-
modified spark ignition engines. It is miscible with most solvents and
sparingly soluble in water [17]. Butanol is produced using fossil fuels,
but can also be produced from biomass, in which case it is called bio-
butanol. Both bio-butanol and petro-butanol have the same chemical
properties [18,19]. Butanol quit similar to gasoline due to the longer
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Renewable and Sustainable Energy Reviews 91 (2018) 394–408
hydrocarbon chain, lower oxygen content and higher heating value of
butanol compared to methanol and ethanol [20]. Butanol can be used in
non-modified spark ignition engines. Furthermore, in the 1930s, the
government of Brazil stimulated gasoline blended with 5% bioethanol
[21]. Due to the first oil crisis in 1973, Brazil decided to establish the
national alcohol program (NAP) to reduce its reliance on fossil oil [22].
In Germany, oxygenated fuel such as MTBE was used with gasoline
since 1985 to improve octane value as well as to decrease engine
emissions. Since that date, the use of MTBE has rose significantly and
reached around 408000–453592.37 Metric Tons in 1997 [23,24].
While MTBE has been used as a gasoline additive in the U.S. by 1979,
formerly it was used as an anti-knock agent to replace lead [25]. DME
does not have a long history as a blending fuel or additive with gasoline
in SI engine, but blending DME into SI engine seems a possible solution
for enhancing the combustion and improving the engine thermal effi-
ciency under normal operation conditions [26,27]. Ethanol was first
submitted as an internal combustion engine fuel by the 1930s in the
USA and became commonly used since 1970 [28]. Currently, ethanol is
used as fuel, especially in Brazil, while in Canada, t USA, and India, also
ethanol is used as a gasoline additive to increase the octane rating and
O.I. Awad et al.
improve engine combustion [29,30]. Due to the issues of gasoline cost
and emission regulations that are becoming more stringent, ethanol
could be given more attention as a renewable fuel or enhancer for
oxygen and octane value.
Ethanol, either neat or as E85 (15% gasoline) has been commer-
cially used for a couple of decades in specific markets, for instance,
Brazil and Sweden. With the arrival of the second oil crisis in 1979,
commercial alcohol-blended fuels were being sold by Chevron, Amoco,
Texaco, and others [31]. Retail sales of gasohol were publicized with
labeling on individual fuel dispensers and the E-10 designation in some
markets. Simultaneously, as the United States started driving out the
lead in gasoline, ethanol became more attractive as an octane enhancer
[20]. Methanol has not got the equivalent level of use as ethanol, but
there is an entirely substantial experience with methanol from various
studies [32,33].
So far, experimental studies [28,34] have claimed that the blending
of methanol or ethanol decreases the engine emissions compared to
fossil fuel especially gasoline. Mainly, in these experimental investiga-
tions, the engine emissions have been associated with the oxygen
content of methanol and ethanol. It is well-known that the chemical and
physical properties of methanol or ethanol are entirely different com-
pared to gasoline. Especially, the heating value of ethanol and methanol
is lower than gasoline. This property explains that the engine will need
more quantity of ethanol or methanol blends to give the same engine
power compared to gasoline. Furthermore, due to the high octane
number of oxygenated fuels, have a high resistance to engine knock,
hence, well satisfied as spark-ignition engine fuels. The decreased en-
gine knock tendencies can be utilized with a high compression ratio,
thereby lead to higher engine power and engine efficiency than pure
gasoline [35]. Another exciting and beneficial property of alcohols and
especially methanol is the comparably high molar expansion that pro-
vides additional pressure during the chemical reactions but without any
additional heat. Furthermore, alcohols offer the highest combustion
efficiency. This is mainly due to the relative oxygen content [8,36,37].
Other than that, the oxygen content of alcohols assists to enhance the
completeness of combustion [14,38]. Alcohol can be used as a pure fuel
in spark ignition engines, but engine modifications are required. Fur-
thermore, alcohol and ether have a significant impact on the environ-
ment and greenhouse gases (GHG) and human health in general
[10,39].
The main objective of this paper is to systematically review of
oxygenated fuels including alcohol and ether regarding production,
environmental impacts and potential using as octane booster of gaso-
line in spark-ignition (SI) engine. Also, another objective is to system-
atically review of the effects alcohols (butanol, methanol, ethanol, and
fusel oil) and ethers (MTBE and DME) on the performance of spark
ignition engine that could potentially replace petroleum-based fuels on
performances (brake power, BSFC, effective efficiency, and EGT) and
emissions (CO, CO2, NOx, and HC), characteristics of spark ignition
engine.
2. Research methodology
2.1. The methodological strategy for the literature review is briefly reported
This paper aims to review the existing research by identifying pat-
terns, themes, and issues, and to discover the conceptual content of the
field. The search was conducted utilizing databases available from
major publishers. Also, the target of this paper is to systematically re-
view the use of oxygenated fuels including butanol, methanol, ethanol,
and fusel oil, MTBE, and DME as fuels in spark ignition engine. In ad-
dition, this paper also discussed an overview of oxygenated production
and the impacts of alcohol fuels to the environment and potential to
replace TEL in gasoline. Furthermore, it was discussed the potential use
some of the oxygenated fuel as an octane booster. Moreover, the current
study has investigated the effects of performance and emissions
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Renewable and Sustainable Energy Reviews 91 (2018) 394–408
characteristics of spark ignition engine with those fuels. Finally, some
of the recommendations were reported.
Various keywords were chosen to achieve an extensive range of
research to be analyzed. The keywords that were selected: oxygenated
fuel; spark ignition engine; alcoholic fuel; ethers fuel; butanol; ethanol;
methanol; MTBE; fusel oil; engine emission; hydrocarbon (HC); carbon
monoxide (CO); carbon dioxide (CO2); nitric oxides (NOx); engine
performance; Tetraethyl lead (TEL), octane number, environment im-
pacts; byproducts food waste. Titles and abstracts of more than 400
papers were chosen and reviewed, and then that relevant papers were
selected based on several criteria and were utilized for this study.
3. The production of oxygenated fuel
In general, oxygenated fuel such as alcohol and ether is produced
from several sources. There are three major pathways for the produc-
tion of alcohols from biomass [40,41]. The first one is fermentation
process by yeast or bacteria. The second one is gasification of lig-
nocellulosic biomass at high temperatures with steam/oxygen to create
synthesis gas, followed by catalyzed reaction of the synthesis gas
components to mixed alcohols. The third one is acid hydrolysis (or
related approaches) of lignocellulosic biomass to produce a range of
five-carbon oxygenates, in some cases requiring subsequent reaction
with an alcohol such as methanol, ethanol, or butanol [15,42]. The
alcohols (methanol, fusel oil, ethanol, butanol, and propanol) are of
interest as fuels because they can be produced biologically or synthe-
sized chemically and have properties that allow them to be used in
internal combustion engines.
In 2014, the United States was the world‫׳‬s largest ethanol fuel
producer, around 60% of global ethanol output. While approximately
23.47 billion Liter was produced by Brazil which represents 25% of the
global production. On the other hand, the European Union only con-
tributed 6% of the global production. China and Canada were the other
leading producers. Fig. 3 shows the global ethanol production by
country, from 2007 to 2015. The production increased dramatically
from 2007 until 2010, while the most significant production was in
2015 after a drop in 2011 and 2012 [43]. In 2013, the production of
ethanol in Turkey was around 73 million Liter according to data given
by the Turkish Tobacco and Alcohol Market Regulatory Authority [44].
Ethanol commonly produced from a biological material through fer-
mentation processes. It can also be produced from petroleum. However,
it is not recommended as it may cause blindness or death [45].
Most methanol is produced from fossil fuels and natural gas. It can
also be produced from biomass using very similar chemical processes.
Alcohol production via gasification is already a very well established
process for methanol production. In fact, most of the methanol pro-
duced nowadays is based on the catalytically conversion of synthesis
gas [46]. Since the 1950s, most butanol in the U.S. is produced com-
mercially from fossil fuels [47]. Butanol can be produced from renew-
able resources employing some organisms including Clostridium acet-
obutylicum [48,49]. Biobutanol may be produced by the
acetone–butanol–ethanol (ABE) fermentation [50]. Bio-butanol has an
advantage in combustion engines as its energy density is closer to ga-
soline than the simpler alcohols (while still retaining over 25% higher
octane rating). However, bio-butanol is currently more difficult to
produce than ethanol or methanol. When obtained from biological
materials and biological processes, it is known as bio-alcohols (bio-
butanol). There are no chemical differences between biologically pro-
duced and chemically produced alcohols. Besides methanol and
ethanol, the most critical alcohols are 1-propanol, 1-butanol, 2-methyl-
1-propanol (isobutyl alcohol), plasticizer alcohols (C6 – C11), and fatty
alcohols (C12 –C18) which are used for detergents. Alcohols are pre-
pared mainly from olefins via the oxo synthesis or by the Ziegler pro-
cess. Most recently in Turkey, about 1 l of acetaldehyde and 5 l of fusel
oil were obtained for every 1000 l of ethyl alcohol from the distillation
process [51]. Furthermore, in Brazil, fusel oil is frequently produced in
O.I. Awad et al. Renewable and Sustainable Energy Reviews 91 (2018) 394–408

Fig. 3. Global ethanol production by country and year 2007–2015.

Source: Renewable Fuels Association [43]

the proportion of 2.5 l per 1000 l of bioethanol production [52]. The programs demand vast quantities of land and water resources [73].
following typical analysis (percentage) of fusel oil from potatoes is Brazil has the most massive program to produce alcohol fuel from
given by Max D. [53]: n- Propyl alcohol 6.85 isobutyl alcohol 24.35 biomass especially ethanol through the fermentation process. In 2005,
amyl alcohol 68.76 acids esters and furfural 0.04. In ordinary molasses to produce 14.99 billion Liter of ethanol through the fermentation
fermentation, about 1 l is recovered for every 1000 l of ethyl alcohol process of sugarcane, approximately millions of hectares of sugarcane
produced, while corns and potatoes yielded slightly higher amounts of fields were used [74]. In 2009, the U.S. projects to divert a third of its
molasses [54]. maize crop to biofuel (ethanol) production. Furthermore, Germany, UK,
The global production quantities of DME in 1996 and earlier are France, and Spain also plan to produce alcohol fuels such as ethanol
around 100 – 150 thousand tons [55,56]. It can be produced from a [75]. The increment in the production of biofuel (alcohol fuels) has a
carbonaceous feedstock, both from renewable sources such as wood, significant impact on the environment and GHG through the increase of
and fossil fuels such as natural gas. Its production method most closely cultivated land area. Land-use change (LUC) is probably the most
resembles that of methanol [57]. MTBE is produced by the chemical controversial issue associated with biofuels including alcohol. The al-
reaction of isobutylene and methanol; therefore, MTBE is derived from cohols have a direct effect on the environment through the direct im-
fossil fuels. Approximately 32,000 m3 per day in 1999 of MTBE was pacts on greenhouse gasses (GHS) reduction by land conversion for
produced in the U.S. during its use as a fuel additive [58,59]. An alcohols feedstock production and the indirect effects on GHG reduc-
overview of alcohol and ether fuels (butanol, methanol, ethanol, fusel tion from off-site land conversion for alcohols feedstock production
oil; MTBE, and DME) production including the raw material and pro- [76]. Another potential environmental benefit of utilizing alcohols fuel
duction processing is listed in Table 1. is the reduction in the liquid waste. The feedstock of alcohol fuels is
waste agriculture [77]. The residuals and by-products generated by
different industrial processes most often have no practical application,
4. Impact of oxygenated fuel on the environment and when stored, may contaminate the environment. Research dedi-
cated to exploring possible uses of these materials is of great importance
Many studies have indicated that the alcohol fuel energy production [40]. Fusel oil as a by-product can not be discarded directly into the
environment since it would cause undesirable environmental impacts
Table 1 [78].
Overview of alcohols and ethers fuel production.
On the other hand, the negative point in the increase of biofuel
Fuel Processing Raw material Ref (alcohols) production on environment presents by requires vast
amounts of land and water resources. Agriculture is a huge water
Ethanol Fermentation Sugar cane [1]
Ethanol Synthesis Gas Coal-derived [60]
spending activity, hectare for hectare, it demands extra water by many
Butanol Synthesis Gas Coal-derived [60] orders of magnitude than is needed for domestic and industrial needs
Ethanol Fermentation Wheat straw [61] for instance in some parts in the U.S. such as in the region of Arizona,
Ethanol Fermentation Mahula (Madhuca latifolia L.) [62] where groundwater is being driven 10 times faster than the natural
Ethanol Synthesis gas CO, CO2, and H2 [63]
recharge potential of the aquifers [79]. These issues, plus the en-
Methanol Synthesis Gas Natural gas [64]
Methanol Synthesis Gas Coke-derived [65] vironmental degeneration and ecological disruptions that affected a
Methanol Biomass gasification Biomass [66] large-scale biofuel cultivation put serious question marks on the sus-
Fusel oil Fermentation Sugar cane and beet [52] tainability of the existing biofuel-to-energy programs [80].
Fusel oil Fermentation Grape Brandy [67] The blending of alcohols with gasoline leads to increased octane
Fusel oil Fermentation Beer [68]
Butanol Fermentation Agricultural residues [69]
rating and is also one of the ways to reduce air emissions problems.
DME Synthesis gas Syngas: coal and biomass [70] These alcohols and MTBE have substituted lead compounds in gasoline
MTBE Catalytic distillation processes Methanol and isobutylene [71] because the use of compounds like TEL in gasoline has produced air
Butanol Fermentation New bacterial strain [72] pollution problems [81]. The use of TEL as an octane booster in

397
O.I. Awad et al.
gasoline creates a unique environmental problem, causing a long-term
exposure of large populations to lead due to the very efficient disper-
sion and accumulation of lead in the human environment. TEL is one of
the most toxic substances that large populations around the world are
exposed to from the exhaust gasses of cars and other sources. Large
social benefits can be achieved by phasing out TEL from gasoline [82].
Alcohols such as ethanol and ethers such as MTBE have been used as
alternatives to replace TEL in gasoline. Moreover, TEL damages the
nervous system and causes brain and blood disorders. The issues will be
further discussed in Section 6 (Alcohols and MTBE as tetraethyl lead
(TEL) replacements).
The emissions from the combustion of the exhausts of vehicles
produce climatic pollution causing severe health hazards [83]. Many
studies consider the role of oxygenated as the fuels for reducing internal
combustion engine emissions. The apparent reduction in the value of
hydrocarbons and CO2 from the exhaust emissions is a real incentive to
make ethanol fuel seriously. The properties of alcohols and gasoline
have a direct influence on the environment. In general, alcohols as fuels
give a better trend to reduce the emission of ICE [84–87] since alcohols
have more oxygen content and lower carbon and sulfur content than
gasoline. Besides, alcohol fuels give higher evaporative emissions due
to higher vapor pressures and low heating value of alcohol which makes
a drop in the performance of engine [88]. Rong-Horng et al., [89]
studied the impacts of ethanol–gasoline on the engine emissions. Based
on the achieved results, the ethanol amount in the blend is more than
20% significantly reduces the hydrocarbon (HC) and carbon monoxide
(CO) emissions.
The most significant properties of oxygenated fueldefine their im-
pacts to the environment are their toxicity solubility and volatility.
Methanol volatilizes into the air due to the high vapor pressure. If re-
leased underground, gas will accumulate in the soil within the pore
spaces, despite it being readily biodegradable. As a volatile organic
compounds VOCs, methanol can contribute to the formation of photo-
chemical smog. Methanol can also be analyzed by sunlight and has a
half-life of 1718 days [90].
Alcohol fuels affect the environment in different ways. Summary of
the impacts are as follows:
• Reduce the dependence on TEL that produces air pollution problems
and health hazards.
• Reduce greenhouse gasses (GHG).
• Reduce air pollution.
• Increased the green land.
• Certain alcohols affect water source in some country [91,92].
• MTBE and certain alcohols affect human health.
5. Adverse impacts of oxygenated fuel
The conventional moisture volumetric content is about 5% when
utilized as dedicated fuel [93,94]. Some alcohols such hydro-ethanol
(4–7%) and fusel oil (5–20%) have high moisture content (water) that is
considered one of the critical properties. The high moisture content and
ash contents in biomass (biofuel) fuels can cause ignition and com-
bustion problems [95]. The moisture content gives adverse effects on
the combustion efficiency, thereby affects engine performance [96–98].
Lanzanova et al. [93] reported the higher moisture content affected
combustion durations, which prolonged both initial flame development
duration and flame propagation duration. Schifter et al. [99] informed
that around 5% of overall engine efficiency was reduced when the
moisture content raised from 20% to 40% per volume due to the pro-
longed engine combustion period. The moisture content has an adverse
effect on decreasing the rate of pressure rise and the low, moisture
concentrations in the fuel appear to have minimum impact on engine
combustion [100,101]. Furthermore, Ambrós et al. [102] announced
that the specific fuel consumption (SFC) of ethanol increases by in-
creasing the amount of moisture content. The in-cylinder and exhaust
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Renewable and Sustainable Energy Reviews 91 (2018) 394–408
temperature are reduced by increasing the amount of moisture in the
fuel. It is noticed that the ethanol with the highest moisture content
blend gives higher pressures at the end of the compression phase. It is
interesting to observe how the slope of the pressure curve decreases
with moisture content in the fuel, suggesting longer combustion dura-
tion.
Moreover, the water content of biomass decreases its heating value
[103]. Demirbas [103] reported that the less heating value of the fuel is
due to the higher moisture content. Moreover, oxygenated fuel espe-
cially alcohols have much less carbon and more oxygen that lead to low
heating value. Demirbas [104] reported that the heating value of the
fuel is associated with its oxygen content and the lower heating value
(LHV) of fuel is reduced by increasing the oxygen and moisture content
while the LHV is increased by increasing the hydrogen and carbon
content. Other disadvantages of oxygenated fuels are vapors lock,
which is caused by the low boiling point and high vapor pressures of
alcohols and ethers. Furthermore, alcohols as good solvents caused
corrosion in some engine parts, and this factor differentiates them with
gasoline in SI engine [105]. Methanol and fusel oil are more corrosive
compared to other alcohols.
Gasoline-alcohol blends are, indeed, a three-component system of
alcohol, gasoline and water. The phase separation temperature (PST)
presents the most significant problem that is related to the main factors
such as water content, gasoline and alcohols composition, and others.
Methanol has limited miscibility to gasoline thereby the phase separa-
tion problem may occur.
Alcoholic fuels have negative impacts on the environment in terms
of a large amount of water consumption as mentioned earlier in section
(impact of oxygenated fuel on the environment). Furthermore, low
combustion enthalpy of alcohols and ethers that are lower than of the
conventional fuel due to the higher oxygen content of the molecules
require a greater injected volume and longer injection time for DME to
supply the same volume of energy that is provided by the conventional
fuel. Moreover, some alcohols have a low viscosity that causes leakage
from the fuel supply system [55]. Typically, the current engines would
require modification to use high concentrations of alcohols [36].
6. Alcohols and MTBE as tetraethyl lead (TEL) replacements
Lead is utilized in many ways, from a bullet to lead-acid batteries,
but its main use over the last decade is as a fuel additive named the TEL,
a compound with the formula CH3CH2 [106]. Numerous engines will
break in less than 50 h under the conditions of heavy knock, and the
damaging effect of knock is cumulative. To prevent the knocking in the
engine, it is necessary to use fuels with high octane number [107].
Straight-run gasoline without lead additives is not suitable for high
compression engines and extra reforming. TEL was discovered as a
highly efficient anti-knock compound. By 1920s, manufacturers started
to improve the engine performance by increasing the compression ratio.
The TEL was blended with gasoline to enhance the octane number so
the blended fuel can be used with high compression ratio [107,108].
Soon after, there was essentially universal acceptance of the need to
eradicate lead from gasoline. Its adverse neurological effects, especially
on human, have been definitively established by many researchers
around the world [109]. In the 1970s, leaded gasoline was outlawed in
the U.S., while in Italy; it has not been sold since 2000 due to a com-
munity law, even if the newer cars use unleaded fuel from the 1990s. At
the moment, almost all countries have banned leaded fuel except some
countries which still use leaded gasoline [110]. Due to the high re-
search and motor octane number of alcohols and ethers, as shown in
Table 4, when alcohols and MTBE are blended with gasoline, the octane
number will increase. Furthermore, alcohols and MTBE have sub-
stituted TEL in gasoline as it causes air pollution. The emissions from
the combustion of transportation exhausts produce climatic pollution
which causes serious health hazards [111–113]. MTBE is a gasoline
additive that was applied permanently as an octane enhancer (4–8% by
O.I. Awad et al. Renewable and Sustainable Energy Reviews 91 (2018) 394–408

Table 2 gasoline by any proportion, and it can be operated in several internal

Contribution of alcohols to gasoline octane number. combustion engines with little or no modification. Alcohols such as
Octane rating TEL concentration (g/ Ethanol volume MTBE volume ethanol have been blended with gasoline in the U.S. for several years
L) ratio (%) ratio (%) [126]. The most familiar gasoline-ethanol blend is the E10 blend which
includes 10% ethanol and 90% gasoline. Moreover, ethanol can be
95 0 0 0
applied as pure (E100) and as a blend of E85 that includes 85% ethanol
96.6 0.2 5 5
97.5 0.3 10 10
and 15% gasoline. Ethanol has an established track record as a neat fuel
98.5 0.5 15 15 in Brazil, where almost five million cars currently run on 190-proof
99.5 0.8 20 20 ethanol (95% ethanol, 5% water) [127]. Ethanol can be utilized as a
99.9 0.9 25 25 primary car fuel in either the neat (pure) or near-neat form [128]. Al-
100 1 30 30
though 100% of butanol could be utilized in SI engine, it probably has a
higher realistic possibility to be blended with gasoline. Many studies
vol) since the phase-out of TEL in the late 1970s [83]. In the late 1980s, recommend that butanol can be blended into either gasoline or diesel to
MTBE usage for octane boosting had grown steadily, followed by its as much as 45% without engine modifications [129,130].
additional application in creating cleaner-burning gasoline for some Methanol 85 (M85) is a blend of 85% methanol and 15% gasoline.
countries. In 1981, MBTE rate was increased to 11% and 15% in 1988. The mixture is utilized to partially mitigate some of the problems cor-
During 1980 and 1986, MTBE usage increased about 40% per year. In related with utilizing methanol (M100) as particularly challenging cold
1984, it was one of the top 50 chemicals manufactured in the U.S. starts at temperatures under 15 °C and also due to safety concerns that
[114–117]. involve in-tank flammability, lack of flame luminosity, and minimal
While the debate about whether MTBE is the best additive for odor or taste [131]. Many studies have been done on the use of ethanol
cleaner gasoline continues, ethanol has appeared as a powerful con- and methanol blends with gasoline by different ratios in SI engines. El-
tender. The production of ethanol has received significant attention Emam and Desoky [132], studied the effects of pure methanol, pure
over the years as an octane booster. Many researchers discussed the ethanol, and other fuels theoretically and experimentally on the com-
possibility to substitute TEL additives with ethanol as it is long re- bustion of spark ignition engines. Their results indicated that the in-
cognized as a good source of octane and accepted in some countries crement in engine thermal efficiency was due to the relatively lower
[81,118–120]. Considering the pollution problems nowadays, in- temperature and peak pressure and the reduction of NOx and CO
vestigations have been concentrated on lowering the concentration of emissions happened when pure ethanol and pure methanol fuels were
toxic components in combustion products. The 0.8 g/l concentration of used. Pourkhesalian et al. [13] investigated the performance and
TEL in gasoline and E20 (20% ethanol-gasoline) blend are used to emissions of the alcohol fuels and pure gasoline in an SI engine. Their
provide a gasoline with an octane number of 99.5 as shown in Table 2. results indicated that the output power and NOx and CO emissions were
Therefore, in bulk, to substitute a ton of TEL would require around 0.3 reduced and the BSFC increased when pure methanol was used instead
MT of ethanol [81,121]. In many countries, methyl tertiary butyl ether of gasoline. Çelik et al. [133] had experiments done on pure methanol
(MTBE) is utilized alternately with TEL to provide gasoline with the and pure gasoline in a four-stroke, single cylinder under different
same octane number. Immediately, 20% volume of MTBE (20% compression ratios (CR) 6:1–8:1 and 10:1 and different engine speeds
MTBE–gasoline blend) is added to unleaded gasoline to provide gaso- (1500–3500 rpm). The knock was not seen at CRs of 8:1 and 10:1 when
line with an octane number of 99.5. However, it is still being used in methanol was used, while the knock was seen at CR of 8:1 when ga-
many countries. Table 3 illustrates some of the advantages and dis- soline was used. The results also indicated that some reductions were
advantages of alcohols and MTBE as octane enhancer additives. found in CO, CO2, and NOx emissions without any evidence of power
loss when methanol was used at CR of 6:1 There are numerous fuel
properties that are important for proper operation of gasoline in spark
7. Oxygenated fuel of SI engine
ignition engines. The addition of alcohol to gasoline affects specific key
properties, mainly blend viscosity, stability, heating value and octane
The blending of gasoline-alcohol has attracted the attention of re-
rating. Corrosiveness and material compatibility are also significant
searchers in many countries including Brazil E5 - E85 (5–85% ethanol),
reasons for consideration. More importantly, any property that affects
Germany (3%, methanol), South -Africa (12 ~01% alcohol blend) and
safety should be foremost in any fuel evaluation, which means that
parts of the USA (10–01% ethanol). Alcohol can be blended with the

Table 3
The advantages and disadvantages of octane enhancer additive.
Octane booster Advantages Disadvantages Ref
additive

MTBE 1. MTBE is utilized as an additive to increase the octane number of MTBE is carcinogenic for humans and animals in drinking water. [122]
gasoline.
2. Oxygen improves the combustion process.
3. Replace the lead (TEL).
Ethanol 1. Increase the octane number of gasoline due to the high octane The lower heating value of ethanol than gasoline led to drop in engine [28,123]
number. performance.
2. Allows running engines with higher compression ratio.
3. Due to the high oxygen content and high octane number the
ethanol lead to shorter burn time and leaner burn engine. It
decreases engine emissions.
4. Replace the lead (TEL).
Methanol 1. Increase the octane number of gasoline due to the high octane The low heating value of methanol than gasoline and ethanol ethanol led [124]
number. to drop in engine performance also caused the problem to start problem
2. Allows running engines with higher compression ratio. of the car in cold weather.
3. Replace the lead (TEL).
Aromatic alcohols 1. alcohols are effective in raising the octane number of gasoline. alcohols are highly carcinogenic and are easily absorbed by the skin. [125]
2. Replace the lead (TEL).

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O.I. Awad et al. Renewable and Sustainable Energy Reviews 91 (2018) 394–408

Table 4
Chemical and physical properties of primary alcohols, ethers, and gasoline.
Gasoline Butanol Methanol Ethanol MTBE DME Fusel oil

Chemical Formula C5–10H12–22 C4H10O CH3OH C2H5OH C5H12O CH3OCH3 C5H12O

CAS Number 86290-81-5 35296-72-1 67-56-1 64-17-5 1634-04-4 115-10-6 8013-75-0
Molecular Weight mass% 106.22 74.12 [134] 32.04 46.7 88.15 46.07 76.42
Carbon mass% 87.5 64.91 37.5 52.2 66.1 52.2 54.8
Hydrogen mass% 12.5 13.49 / 34.7 13.7 13 15
Oxygen(a) mass% 0 21.6 49.93 34.7 18.2 34.8 30.32
Density, (g/ml) 0.737 0.810 0.792 0.785 0.74 0.661b 0.847
Boiling temperature, °C 27–225 117.25 78 78.25 [135] 52.2 − 25.1 [136] 53.4–54.4
Reid vapor pressure, Kpa 53–60 18.6 [137] 32.4 17 54.47 / /
Research octane no. 90–100 98 108.7 108.6–110 118 [138] / 106.85
Motor octane no. 82–92 78 86.6 92 102 / 103.72
LHOV kJ/kg 349 [139] 707.9 920 923 320 [140] / /
LHV MJ kg− 1 44.0 33.2 20.1 26.9 34.9 28.8 29.536
Freezing point, °C − 40 / − 97.5 − 114 − 108 / − 52
Viscosity mm2/s 0.5–0.6 / 0.596 1.2–1.5 0.35 / 0.61
Flash point, °C − 45to − 13 / 11 12–20 − 25.5 / /
Autoignition temperature, °C 257 385 423 425 435 253 41.6

flammability and flashpoint should be considered.
8. The effect of oxygenated fuels on engine emissions
Engine emissions such hydrocarbon (HC) Carbon monoxide (CO),
Carbon dioxide (CO2 (and nitric oxides (NOx) in spark ignition engines
are related to engine operating condition and fuel properties. The re-
lationships have been investigated for a variety of alcohol and gasoline
in spark ignition engines. The alcohol used in internal combustion en-
gines can effect on exhaust engine emission and toxic exhaust compo-
nents [157–159]. The impact of alcohol fuel on HC, CO, CO2, and NOx
emissions that have been listed in the literature are comprehensively
summarized in Tables 6–9, respectively, which include different alcohol
fuels, test conditions and the effects of alcohol on the emission. Some of
the studies that listed in the tables and others are described in the
following sections.
8.1. Effect on NOx emission
As described in Table 5, almost the NOx emission decreased with
oxygenated fuels in compared with pure gasoline. However, the op-
eration condition affected on the NOx emission. Calam et al. [160]
reported that the NOx emissions decreased when fusel oil used com-
pared with gasoline. This could be explained by the higher water and
oxygen content of fusel oil. Furthermore, Al-Baghdadi [161] informed
the peak in-cylinder temperature decreased when alcohol used gasoline
due to its high heat of vaporization. Therefore NOx emission decreased.
Zervas et al. [162] studied the impact of fuel composition and
equivalence air-fuel ratio on NOx emissions. Their results concluded
that at stoichiometry condition, alcohol blends of 2-propanol, ethanol,
methanol, and MTBE with gasoline by 5% and 20% volume could re-
duce up to 60% NOx emission. Moreover, the blending of butanol and
ethanol with gasoline significantly reduced the NOx emission that re-
ported by [144].
Overall, more attention has been given to engine load than speed
most seemingly due to its more significant impact on the combustion
temperature. Wang et al. [163] used different fuels including DMF,
ethanol, and gasoline experimented on a single cylinder gasoline engine
under 1500 rpm engine speed, the stoichiometric air-fuel ratio (AFR)
and different engine loads (3.5 and 8.5 bar IMEP) and MBT. The high
oxygen content and high molecule combustion temperature of alcohol
promote the availability of oxygen for combustion, hence improving
combustion efficiency. Next, high in-cylinder temperature caused
higher NOx emissions by DMF and ethanol, by 50% and 25% respec-
tively, compared to gasoline when the engine at high load. Ji et al.
[147] modified a spark ignition engine to run on DME-gasoline blend
and found that NOx and HC emissions increased with increasing DME
content in the blend. While Turner et al. [164] investigated the impact
of methanol–ethanol-gasoline blends on NOx and CO2 emissions. The
various blend ratios used to operate an SI engine and found that dual
fuel blends could reduce CO2 and NOx emissions to be lesser than that
produced by pure gasoline.
8.2. Effects on CO emission
Carbon monoxide (CO) and unburned hydrocarbon (UHC) emis-
sions are among the exhaust gasses which describe the loss of chemical
energy due to incomplete combustion in the engine. Indeed, if the
combustion temperature through combustion process is not enough to
support the complete combustion, thereby the transformation of CO to
CO2 will not happen [165]. The CO level is hugely dependent on
oxygen content and air-fuel ratio relative to the stoichiometric pro-
portions [166]. Many studies have been conducted on the correlation
between various types of alcohol as blends or additives for gasoline and
CO emission in spark ignition engines. Several researchers have shown
that the reduction in CO emissions could happen when using alcohol as
fuel. According to the previous researchers listed in Table 6, the CO
emission decreased with oxygenated fuels except for fusel oil compared
with pure gasoline. Moreover, the study that achieved by Masum et al.
[139] also indicated the blending of alcohols-gasoline had lower CO
and HC emissions compared with gasoline. Bata et al. [167] in-
vestigated various ethanol-gasoline blend ratios in a spark ignition
engine, and as stated that ethanol could decrease CO and HC emissions
to some degree. The decrease of CO emission is apparently due to the
wide flammability and oxygenated characteristic of ethanol. In the
study by Palmer [168], he showed that increasing ethanol concentra-
tion in gasoline by 10% led to decreased CO emission by up to 30%.
Moreover, Rice et al. [169] experimented with a spark-ignition engine
running on ethanol-gasoline,isobutanol-methanol-gasoline and gasoline
fuel. As results, were shown that the CO emission decreased with al-
cohol blends compared to gasoline. This result was associated with the
lower stoichiometric A/F value for alcohol, and it was coupled with the
lowering of peak combustion temperature for alcohol blends. The ef-
fects of various compression ratios, CR (6:1, 10:1 and 13:1) with alcohol
fuels was studied by [170]. This experiment was performed on a four-
stroke single cylinder engine at different ethanol ratios with gasoline
(E25, E50, E75, and E100), constant load and speed. The level of CO
emission with E50 was lower by 54% than that of pure gasoline at the
same CR because CO emission is primarily related to air-fuel ratio. Due
to increased ethanol concentration in the blend, the oxygen con-
centration increased. Thereby CO emission decreased due to oxygen
enhancement. Additionally, when the engine was running on E50 at

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O.I. Awad et al. Renewable and Sustainable Energy Reviews 91 (2018) 394–408

high CR (10:1 and 13:1), CO decreased when using E50 compared to

Reference
E50 at a compression ratio of 6:1. A 53% reduction in CO emission was
[141]

[142]

[143]

[144]

[145]

[146]

[147]

[148]

[149]
[150]
achieved with E50 blend at a CR of 10:1 compared to CR 6:1. Song et al.
[171] investigated the impact of adding ethanol content (up to 9.79%
2013

2102

2013

2016

2013

2015

2011

2000

2015
2015
Year

ethanol) and MTBE (up to 20%) in gasoline and found that CO and HC
emissions decreased as compared to using MTBE.

NOx emission decreased significantly across the CR range with the addition of

speed, the addition of MTBE had no significant effect on NOx emission, which
In general, MTBE blends caused higher NOx emission when using rich fuel and
ethanol and butanol to gasoline, with ethanol being the most significant effect.
NOx emission decreased by 43% when ethanol was added to gasoline, which

n-butanol-gasoline blends and pure n-butanol reduced NOx emission than

8.3. Effect of oxygenated fuel on CO2 emission

stoichiometric mixtures, but lower emission when using lean fuel. At idle
The maximum reduction in NOx emission was with E85 by about 15%.

Ethanol and methanol increased NOx emission compared to gasoline.

NOx emission increased by 16.18% with increasing blending ratio.
those of gasoline. Furthermore, EGR could decrease NOx emission

Although carbon dioxide (CO2) is a non-toxic gas and is not classi-

fied as an engine pollutant, it is one of the substances that are re-

NOx emission clearly reduced with increasing DME amount.

sponsible for rising global temperature through the greenhouse effect
[154]. CO2 is produced by the complete combustion of hydrocarbon
was applied in a high concentration of ethanol E15.

fuel. The CO2 formation is influenced by the (C-H) ratio in fuel. Ad-
NOx emissions decreased when fusel oil was used

ditionally, oxygen content plays the main role in improving engine

Butanol-gasoline blends reduced NOx emission

combustion, which increases the CO2 level and is obviously occurring in

oxygenated and alcohol fuels. According to the study that listed in
Table 7, at almost the CO2 emission increased with oxygenated fuels
compared with pure gasoline. Canakci et al. [155] study the impact of
different MTBE blending ratios (10%, 15% and 20%) with gasoline on
engine performance and pollutant in a gasoline engine. It was found
Effect on NOx emission

was readily very small.

higher CO2 exhaust emission with MTBE–gasoline blend, which is an

evidence of its better combustion capability than pure gasoline. This
result could be associated with lower number of carbon atoms than the
average carbon number of pure gasoline, 5 and 8 atoms, respectively.
Shahad and Wabdan [149] observed 7.5% increase in CO2 emission
with increasing speed and load, compared to using gasoline, while CO2
reduced with increasing compression ratio. Due to high oxygen content
The operation was achieved by the negative valve overlap

in ethanol, the oxygen ratio in the blend increased, leading to lean

Various engine speeds (1000–3000 rpm), spark ignition
strategy through VEAIVT and lift devices. Also at VES

combustion. Consequently, CO2 emission increased because of the im-

Under stoichiometric air/fuel ratio, 1400 rpm engine
Under stoichiometric air/fuel ratio at various engine

proved combustion [172]. Furthermore, CO2 emission decreased when

alcohol was used in fumigation mode compared to fossil fuels [173].
Ozsezen and Canakci [174] reported 0.1% increment in CO2 emission
Various injection timing and engine loads
Various engine speeds and engine loads.

Various engine speeds, torques, and CR

when using E5 and E10 on four cylinders spark ignition 4 C engine.

Various spark timings and EGR rates

Various spark timings and EGR rates

Balki et al. [175] noticed 2.51% increment in CO2 when using pure
Various speeds and engine loads

ethanol in a gasoline engine. The similar slight increase in CO2 emission

was also reported in several studies [176–180].
speeds and engine loads.

and equivalence ratio.

8.4. Effects on HC emission

Test condition

Due to the studied that listed in Table 8, at almost the HC emission

decreased with oxygenated fuels compared with pure gasoline. Fur-
speed

thermore, the impact of utilizing ethanol-gasoline blends on the HC

emissions as compared to with pure gasoline was studied by [89]. Ac-
cording to the results, higher than 20% ethanol concentration in the
1.6 L, 4 C, 4 S, SI engine port
SC, 4 S, SI engine port-type

2.96 L, 6 C, 4 S, l SI engine
HCCI / CAI with CR 10.66
3 C,4 S, port fuel injection,

3 C,4 S, port fuel injection,

The effect of alcohol and ether fuels on NOX emission in SI engines.

SC,4 S, port fuel injection,

blend reduced the engine's first operation HC emission significantly

SC 4 S, WC, dual Fuel.

compared to gasoline. Kisenyi et al. [181] examined the impact of

fuel infection system
fuel injection system
4 C, 4 S, SI engine

MTBE additive (15% v/v) in gasoline on engine emissions, in which the

SC 4 S, air cooled
SI engine type

result revealed that MTBE decreased HC by 10–20%. Qi and Lee [182]

with CR 9.6

with CR 9.6

informed that the HC emission of ethanol blends (E10 and E20) were
relatively close to pure gasoline at lower engine loads but higher at
SC 2 S

higher engine loads. Ji et al. [136] experimented under idle and stoi-
chiometric conditions to study the impact of adding DME on the idle
Bu0, Bu10, Bu30, Bu40,

Bu0, Bu10, Bu30, Bu40,

performance of SI ethanol engine. As a result, HC emission reduced

MTBE15, and MTBE20
Bu0, Bu30, and Bu100

F0, F10, F20 and F30.

E0, E10 E15 E20, E30

with increasing amount of added DME. A four-cylinder SI engine was

MTBE0, MTBE10,
E5, E10, and E15

E5, E10 and E15

used by [86] which ran under various compression ratio and speed
Blending ratio

and E85 Bu10

DME (0–30%)

E10 and M10

fueled by various ethanol-gasoline blends. They found that the reduc-

and Bu100

and Bu100

tion in HC emission happened at 1500 and 5000 rpm at both com-

pression ratios when ethanol was added. The minimum HC emission
was reported when using E85l, while the highest HC emission was re-
ported when using pure gasoline.
Methanol Ethanol
Alcohol types

Bio-ethanol n-
butanol

9. The effect of oxygenated fuels on SI engine performance

n-butanol

n-butanol

n-butanol
Methanol

Fusel oil

Ethanol
Table 5

MTBE
DME

The performance characteristics of spark ignition engines are di-

rectly affected by the type of fuel used. These characteristics include

401
 O.I. Awad et al.

Table 6
The effect of alcohol and ether fuels on CO emission in SI engines.
Alcohol type Blending ratio SI Engine Type Test condition Effect on CO emission Year Reference

Ethanol E5, E10, and E15 SC 4 S, WC, dual Fuel. Various engine speeds, torque, and CR Ethanol blends decreased CO emission by about 45% 2015 [149]
Methanol Ethanol E10 and M10 SC 4 S, air cooled Various injection timing and engine loads E10 had lower CO emission compared to gasoline. 2015 [150]
Methanol E5, E10, and E15 SC 2 S Various speeds and engine loads CO reduced by around 71% when 15% ethanol was added to gasoline. 2013 [141]
n-butanol Bu0, Bu10, Bu30, Bu40, 3 C,4 S, port fuel injection, Various spark timings and EGR rates n-butanol-gasoline blends decreased CO emission, while pure n-butanol 2012 [142]
and Bu100 with CR 9.6 increased CO emissions compared to those of gasoline. Furthermore,
advancing spark timing reduced CO emission
isobutanol iB0, iB3, iB7 and iB10 SC,4 S 2 valves, air-cooled, Various engine speeds CO emission by pure gasoline was greater than butanol-gasoline blends at 2015 [151]
carbureted 2900 rpm or slower, but, the opposite occurred for speeds higher than
2900 rpm
Bio-ethanol n- E0, E10 E15 E20, E30 and 4 C, 4 S, SI engine Various engine speeds and engine loads. The maximum reduction in CO emission was related to E85 by about 15% 2013 [145]
butanol E85 Bu10

402
Fusel oil F0, F10, F20 and F30. SC, 4 S, SI engine port-type Under stoichiometric air/fuel ratio at various engine CO emission increased with increasing amount of fusel oil. 2015 [146]
fuel injection system speeds and engine loads.
DME DME (0–30%) 1.6 L,4 C, 4 S, SI engine port Under stoichiometric air/fuel ratio, 1400 rpm engine CO emission first reduced and then increased as the concentration of DME was 2011 [147]
fuel injection system speed and a manifold absolute pressure (MAP) of 61.5 kPa increased. The largest reduction in CO emission for DME-gasoline blends was
10% at 12.4% DME energy fraction compared to gasoline.
MTBE MTBE0, MTBE2, MTBE5, 1.6 L, 4 C, 4 S, Opel SI Various speeds (1000–2500 rpm) and engine power (0–20 CO emission decreased at high engine load when 11 w/w% of MTBE was 2000 [152]
MTBE8 and MTBE11 engine HP) added to gasoline
MTBE MTBE0, MTBE10, 2.96 L, 6 C, 4 S, l SI engine Various engine speeds (1000–3000 rpm), spark ignition CO emission decreased with increasing MTBE ratio. Also, leaded fuel caused 2000 [148]
MTBE15, and MTBE20 and equivalence ratio. higher CO emission compared to MTBE blend.
Methanol and M100 and E100 4 C, 4 S, WC engine Various CR (6 – 16), equivalence ratio, and ignition Ethanol and methanol reduced the concentration level of CO emission 1985 [132]
ethanol timing was set to 20° before TDC.
Methanol and M100 and E100 4 C, 4 S, naturally aspirated Various engine speeds with CR of 8.6 Alcohol reduced CO emissions due to H/C ratio. 2010 [13]
ethanol engine
ethanol E25, E50, E75 and E100 4 C, 4 S, high CR engine Various CR at constant load and speed CO emission decreased with ethanol due to its high oxygen content. 2008 [153]
Renewable and Sustainable Energy Reviews 91 (2018) 394–408
 Table 7
The effect of alcohol and ether fuels on CO2 emission in SI engines.
Alcohol type Blending ratio SI Engine Type Test condition Effect of CO2 Year Reference
O.I. Awad et al.

Ethanol E5, E10, and E15 SC 4 S, WC, dual Fuel. Various engine speeds, torque, and CR Ethanol blend increased CO2 emission by 7.5% 2015 [149]
Methanol E5, E10, and E15 SC 2 S Various speeds and engine loads CO2 emission increased by 6.3% on average by incrementally increasing 2013 [141]
ethanol concentration by 5% at different loads and speeds
isobutanol iB0, iB3, iB7 and iB10 SC,4 S 2 valves, air-cooled, Various engine speeds CO2 emission produced by isobutanol–gasoline blends was always lower by up 2015 [151]
carbureted to 43% compared to gasoline at all speed
DMF Pure DMF 4 C,4 S,4 valves DISI engine Stoichiometric AFR (λ = 1) with fixed injection timing CO2 emission decreased when using DFM compared to gasoline 2012 [154]
(280° BTDC) and various spark timing
MTBE MTBE10, MTBE20 and SC, 4 S DISI engine Various speeds and engine loads CO2 emission increased when using MTBE compared to gasoline 1993 [155]
MTBE30
Ethanol and E5, E10, M5, and M10 4 C, 4 S, an engine with Under two vehicle speeds (80 and 100 km/h), and four CO2 emissions decreased at low speed, while it increased at high speed when 2013 [156]
methanol MPFJS engine loads using alcohol-gasoline blends (E5, E10, M5, and M10)

403
Table 8
The effect of alcohol and ether fuels on HC emission in SI engines.
Alcohol type Blending ratio SI Engine Type Test condition Effect on HC Year Reference

Ethanol E5, E10, and E15 SC 4 S, WC, dual Fuel. Various speeds and CR Ethanol blend had decreased HC emission by about 40.15%. 2015 [149]
Methanol Ethanol E10 and M10 SC 4 S, air cooled Various injection timings and engine loads E10 produced lower UHC emission than gasoline 2015 [150]
Methanol E5, E10, and E15 SC 2 S Various speeds and CR Ethanol reduced HC emission in all cases; the reduction was around 6%. 2013 [141]
n-butanol Bu0, Bu10, Bu30, Bu40, 3 C,4 S, port fuel injection, Various spark timings and EGR rates n-butanol-gasoline blends had decreased HC emission. Furthermore, 2012 [142]
and Bu100 with CR 9.6 advancing spark timing increased HC emissions
isobutanol iB0, iB3, iB7, and iB10 SC,4 S 2 valves, air-cooled, Various engine speeds Butanol-gasoline blends had reduced UHC emission at 2900 rpm or lower. 2015 [151]
carbureted However, pure gasoline produced lower UHC emission than the blend at
speeds higher than 2900 rpm.
n-butanol Bu0, Bu10, Bu30, Bu40, 3 C,4 S, port fuel injection, Various spark timings and EGR rates The addition of ethanol and butanol in gasoline significantly decreased HC 2016 [144]
and Bu100 with CR 9.6 emission across the CR range.
Bio-ethanol n- E0, E10 E15 E20, E30 and 4 C, 4 S, SI engine Various engine speeds and engine loads. Maximum reduction of THC was related to E85, that was around 20%. 2013 [145]
butanol E85 Bu10
Fusel oil F0, F10, F20 and F30. SC, 4 S, SI engine port-type Under stoichiometric air/fuel ratio at Various engine Increasing the amount of fusel oil increased HC emission 2015 [146]
fuel injection system speeds and engine loads.
DME DME (0–30%) 1.6 L,4 C, 4 S, SI engine port Under stoichiometric air/fuel ratio, 1400 rpm engine speed HC emission reduced with increasing DME amount. 2011 [147]
fuel injection system and a manifold absolute pressure (MAP) of 61.5 kPa
MTBE MTBE0, MTBE2, MTBE5, 1.6 L, 4 C, 4 S, Opel SI Various speeds (1000–2500 rpm) and engine power (0–20 HC emission decreased at high engine load when 11 w/w% of MTBE was 2000 [152]
MTBE8 and MTBE11 engine HP) added with gasoline
MTBE MTBE0, MTBE10, 2.96 L, 6 C, 4 S, l SI engine Various engine speeds (1000–3000 rpm), spark ignition HC emission decreased with increasing MTBE ratio. 2000 [148]
MTBE15, and MTBE20 and equivalence ratio.
Renewable and Sustainable Energy Reviews 91 (2018) 394–408
O.I. Awad et al. Renewable and Sustainable Energy Reviews 91 (2018) 394–408

engine power, SFC and brake thermal efficiency (BTE). The influence of
Reference
alcohol and ether-based oxygenated fuel on the performance char-
[132]

[163]

[160]

[187]

[190]

[155]

[163]

[182]

[187]
[190]
[26]

[13]
acteristics of SI engines as described in the literature are summarized in
Table 9 and are comprehensively reviewed in this section. The review
ISFC increased when using DMF and ethanol due to lower heating value for ethanol and DMF compared to

Engine full load torque clearly increased for all speeds lower than 7000 rpm, but maintained the same for

BSFC increased with ethanol (49%) and methanol (80%) compared to gasoline due the high heating value
Alcohols (ethanol and methanol) had slightly higher ITE compared to gasoline and other fuels used in this

DME increased thermal efficiency by over 20% compared to pure gasoline. Also, the flame development

At 8.5 bar IMEP, ethanol showed the highest thermal efficiency (38.5%), while it was 37% for DMF and
includes different engine types, alcohol fuel blends, test conditions and
Engine torque increased slightly with increasing ignition timing. Also, engine efficiency increased with

BSFC increased when using MTBE as a blending fuel for speed ranging between 2800 and 5000 rpm

BSFC increased when using ethanol-gasoline compared to gasoline, and it increased with increasing
the effects of alcohol and ether on power, torque, SFC and brakes

Engine torque increased by 1.44%, 1.86%, and 3.2% for F10, F20 F30 compared to pure gasoline
thermal efficiency (BTE).
Some studies have shown that engine torque increased slightly, but
fuel consumption increased when using alcohol fuels. This is because

BSFC increased for all engine speeds depending on the quantity of fusel oil in the blend.
alcohol has less energy per unit volume compared to gasoline. The
engine power and torque depend heavily on an engine's in-cylinder
pressure. Calam et al. [183] experimented on a four-stroke, single cy-
linder, SI Hydra engine, which ran at different engine speeds (1500,
2500, 3500 and 5000 rpm), different engine loads 25%, 50%, 75%, and
test due to the relatively lower pressure and in -cylinder temperature

100% and different test fuels (F0, F10, F20 and F30). The torque in-
creased in all loads and engine speeds when the amount of fusel oil in
and propagation periods decreased with the addition of DME

each test fuel was increased. Chongming et al.[163] used three fuels
DMF, ethanol, and gasoline on a single cylinder, spray-guided, 4-stroke
Impact on engine power, thermal efficiency, and BSFC

BSFC decreased by 14% on average when using B35 DISI research engine at 1500 rpm engine speed, the stoichiometric air-
fuel ratio (AFR) and different engine loads between 3.5 and 8.5 bar
IMEP, as well as using the fuel-specific optimum spark timings (MBT). It
increasing amount of fusel oil in the blend

was found that at 8.5 bar IMEP engine load, the combustion duration
for DMF was shorter than gasoline and ethanol by 4 and 1 crank angle
engine speeds higher than 7000 rpm,

degree, respectively. DMF generated the highest in-cylinder peak

pressure, which was higher than that of ethanol. DMF and ethanol had
greater ant-knocking than gasoline due high octane number. At 8.5 bar
IMEP, the highest thermal efficiency was obtained when using ethanol
(38.5%), while DMF and gasoline had 37% and 36%, respectively.
36% for gasoline.

ethanol content.

Significant research has been achieved to quantify the ability of fuel

octane rating to provide higher power, torque, and engine efficiency by
gasoline.

increasing compression ratio (CR) in spark-ignited engines

[86,184,185]. High octane value and high latent heat of vaporization
(LHOV) of alcohol make it a suitable fuel for high compression ratio
engine, which produces high-output power. High octane rating can
Various CR (6 – 16), equivalence ratio and The ignition timing

under 1500 rpm speed, stoichiometry (AFR) and various engine

Under 1500 rpm speed, stoichiometry (AFR) and Various engine

allow for a high compression ratio and provides higher performance.

Various engine speeds. (2500, 3000, 3500, 4000, 4500 and
Under idle and stoichiometric conditions and CR of 10:1

Yücesu et al. [179] studied the impact of gasoline, E10, E20, E40, and
The effect of alcohol and ether fuels on engine power, thermal efficiency and BSFC in SI engines.

Various engine speeds, full engine load and CR of 11

E60 on the performance of spark ignition engine with CR between 8:1

and 13:1. It was found that engine torque and power increased when
ethanol was used at higher CR. Heywood [186] discussed the impact of
CR on the performance of an eight cylinder 5.3-litre engine at 2000 rpm
Various engine speeds (3000–8000 rpm)

Various engine speeds (3000–8000 rpm)

at full load condition. Yang [187] investigated the effect of buta-

Various engine speeds and part load
Various engine speeds with CR 8.6

nol–gasoline blend (B35) on engine performance, in which found that

Various speeds and engine loads

the engine full load torque increased for all speed lower than 7000 rpm
using B35 compared to gasoline. While for engine speed faster than
was set to 20 before TDC.

7000 rpm, the full load engine torque maintained the same.
Various spark timings

The experiment performed by Calam A. et al., [160] with different

gasoline- fusel oil blends (B0, F5, F10, F20, F30, and F50) under full
Under full load
Test condition

load condition, running at 3500 rpm maximum engine torque with

5000 rpm)

different advance values. It was shown that adding fusel oil into gaso-
loads

loads

line lowered the calorific heat value of fusel oil (almost 30% lower than
unleaded gasoline) led to lower calorific heat value of the test fuels. As
a result, the brake specific fuel consumption (BSFC) also increased.
F0, F5, F10, F20, F30 and

MTBE10, MTBE20 and

Abu-Zaid et al. [188] investigated the impact of methanol-gasoline

F0, F10, F20 and F30.

F0, F10, F20 and F30.

blends on engine performance. The tests were conducted under the

DMF100 and E100

DMF100 and E100

M100 and E100

M100 and E100

condition of full open throttle (WOT) and various engine speeds from
Blending ratio

DME 0–100%

E10 and E20

1000 to 2500 rpm using different methanol-gasoline blends. As a result,

MTBE30

the brake specific fuel consumption increased for all engine speeds and
blending ratios compared to pure gasoline, except when using E15.
B35

B35
F50

Furthermore, Costa and Sodré [177] indicated that BSFC increased by

50–70% with Hydrous ethanol compared to gasoline. Similar results
Methanol and ethanol

Methanol and ethanol

were also achieved in other studies [179,189].

DMF and ethanol

DMF and ethanol

Qi and Lee [182] found that brake thermal efficiency (BTE) of the
Alcohol type

ethanol-gasoline blends was similar to pure gasoline, but BSFC was

Fusel oil

Fusel oil

Fusel oil
Butanol

Butanol
Ethanol

higher compared to gasoline. Balki et al. [175] mentioned that the

Table 9

MTBE
DME

using methanol and ethanol significantly increased BSFC due to the

lower heating value of methanol and ethanol. Furthermore, Icingur and

404
O.I. Awad et al.
Calam [190] stated that specific fuel consumption (SFC) increased for
all engine speeds depending on the quantity of fusel oil in the blend.
The highest increment in SFC (7.7%) was obtained with F30. Moreover,
Osman et al. [155] reported that the brake specific fuel consumption
increased when MTBE was used as a blending fuel at speeds ranging
between 2800 and 5000 rpm. Under the same range of speed, the BSFC
of MTBE was closed to pure gasoline. This result could be due to the
higher energy value (heating value) and lower density of the gasoline
compared to MTBE. Furthermore, fuel with a higher octane number can
endure higher compression ratios before an engine starts knocking, thus
giving an engine the ability to deliver more power efficiently and
economically. Oxygenated fuels with high octane value permits in-
crease of compression ratio and can provide higher density of fuel-air
mix. The increase in compression ratio improves engine power output
and efficiency. Improvements in engine performance by means of in-
creasing compression ratio is limited by knocking in gasoline-powered
engines [188,191].
10. Recommendations
Many factors should be considered before recommending the utili-
zation of an alternative fuel for existing technologies at a large scale.
Researchers have discussed the factors and few of the significant factors
are explained as follows:
• The environmental compatibility of an alternative fuel as compared
to fossil fuels should be observed. If the alternative fuel has very
high emissions compared to fossil, it would be unacceptable for
usage as fuel [36].
• Additional cost on the user in terms of routine maintenance,
equipment wear and tear, and lubricating oil's life must be observed.
The excessive additional cost will have an adverse impact on the
widespread acceptance of this fuel [36].
• Alcohol production is simple and eco-friendly. It can be produced
locally, hence cutting down the fuel transportation price.
Furthermore, it can be utilized immediately in an engine or it can be
blended with gasoline [192].
• Alcohol water content such as in fusel oil should be extracted when
utilizing it as fuel.
• It is not important to repeat detailed of performance and emission
assessments of SI engine. Depending on ethanol, methanol, and
butanol without and additive or engine modification, in various
cases, it will be possible to get a sufficiently reliable evaluation from
the previous study. On another hand, should focus on the others fuel
such as fusel oil.
• Attention must be paid to gathering the enhancement of the gasoline
properties by using oxygenated fuel.
11. Conclusion
Alcohol and ether-based oxygenated fuels play an increasingly sig-
nificant role in meeting the energy demand in the automotive sector. In
this literature review, information on various types of alcohol (butanol,
methanol, ethanol, and fusel oil) and ether (MTBE, and DME) that using
as fuel in SI engine have been summarized in term of its production,
environmental impacts and potential using as octane booster of gaso-
line. Also, have been summarized the effects of oxygenated fuels on
performances and emissions (CO, CO2, NOx, and HC), characteristics of
spark ignition engine.
Oxygenated fuels have a promised future since are renewable and
produced from several sources also can be produced locally. Alcohol
and ether have a significant impact on the environment and greenhouse
gasses (GHG) and human health in general. Furthermore, alcohol and
ether produce clean burning compared to gasoline and produce lower
carbon monoxide (CO) and oxides of nitrogen (NOx). The CO2 forma-
tion is influenced by the (C/H) ratio and oxygen content in fuel.
405
Renewable and Sustainable Energy Reviews 91 (2018) 394–408
Therefore, CO2 formation increases clearly with oxygenated fuels.
Nevertheless, ethanol could decrease the carbon monoxide (CO) and
hydrocarbon (HC) emissions to some level, in which the decrease in CO
emission is due to the wide flammability and oxygen content of ethanol.
Due to the high-octane number of MTBE and ethanol have been used as
alternative solutions to replace TEL (Tetraethyllead) additives as an
octane booster.
Engine torque and power increased slightly when using alcohols
fuel, while fuel consumption increased significantly. It has been proven
in significant research octane rating has the ability to provide higher
power, torque, and engine efficiency by increasing the compression
ratio. A fuel with a higher octane rating can endure higher CR before
the engine starts knocking, therefore enabling the engine to produce
more power efficiently and reduce fuel consumption.
Overall, oxygenated fuels have been found to be a very promising
alternative fuel for SI engines, capable of providing high thermal effi-
ciency and lower NOx levels. The water content of fusel oil and hydro-
ethanol has played negatively to limited the heating value, and per-
formance of the fuel blend despite the high oxygen content of oxyge-
nated fuel thereby should remove it before utilizing as a fuel in SI en-
gine.
Acknowledgments
The financial support offered by the Universiti Malaysia Pahang
under RDU 160309 and RDU172204 are gratefully acknowledged
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.rser.2018.03.107.
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