Renewable and Sustainable Energy Reviews 60 (2016) 84–115

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Renewable and Sustainable Energy Reviews

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

Use of higher alcohol biofuels in diesel engines: A review

B. Rajesh Kumar a,n, S. Saravanan b,1
a
IC Engines Division, Department of Mechanical Engineering, Jeppiaar Institute of Technology, Chennai, TN, India
b
Engine Research Lab, Department of Mechanical Engineering, Sri Venkateswara College of Engineering, Chennai, TN, India

art ic l e i nf o a b s t r a c t

Article history: Biofuels have grabbed the attention of engine researchers ever since the oil-crisis and escalating costs of
Received 10 September 2015 petro-chemicals cropped up in the '70s. Ethanol and methanol were the most widely researched alcohols
Received in revised form in IC engines. However, the last decade has witnessed significant amount of research in higher alcohols
28 December 2015
due to the development of modern fermentation processes using engineered micro-organisms that
Accepted 14 January 2016
improved yield. Higher alcohols are attractive second/third generation biofuels that can be produced
Available online 2 February 2016
from sugary, starchy and ligno-cellulosic biomass feedstocks using sustainable pathways. The present
Keywords: work reviews the current literature concerning the effects of using higher alcohols ranging from 3-
Diesel engine carbon propanol to 20-carbon phytol on combustion, performance and emission characteristics of a wide
Bio-alcohols range of diesel engines under various test conditions. The literature is abound with evidence that higher
Butanol
alcohols reduce carcinogenic particulate emissions that are prevalent in diesel engines. NOx emissions
Pentanol
either increased or decreased based on the domination of either cetane number or heat of evaporation.
Performance
Emission
Brake specific fuel consumption (BSFC) of the engine usually suffered due to low energy content of
alcohols. A notable feature is that the combination of higher alcohols (like butanol or pentanol), high
exhaust gas recirculation (EGR) rates and late injection timing enabled low temperature combustion
(LTC) in diesel engines that can simultaneously reduce smoke and NOx emissions with improved engine
efficiency. It can be concluded that higher alcohols reduce smoke emissions with their fuel-borne oxy-
gen; enhance air/fuel mixing by offering long ignition delay and eventually replace fossil diesel (partially
or wholly) to enable a clean and efficient combustion in compression-ignition engines. The chief thrust
areas include developing mutant strains with higher yield, higher tolerance to toxic inhibition and low-
cost substrates for fermentation. Further work is required in stipulating optimum blend-fuel character-
istics and ensuring the long-term durability of the engines using these fuels.
& 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2. Propanol in diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2.1. Combustion, performance and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.2. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.3. Future research directions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3. Butanol in diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.1. Comparative behavior of butanol isomers in diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2. Diesel/butanol blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2.1. Combustion, performance and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2.2. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.2.3. Future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

Abbreviations: CA, Crank Angle; CI, Compression Ignition; CN, Cetane Number; CO, Carbon Monoxide (% volume); CO2, Carbon Dioxide (% volume); DI, Direct-Injection; HC,
Hydrocarbon (ppm volume); HCHO, Formaldehyde; HCOOH, Formic acid; NOx, Nitrogen Oxides (ppm Volume); PPM, Parts Per Million; rpm, revolutions per minute; v/v, per
volume
n
Corresponding author. Tel.: þ 91 4427269072.
E-mail addresses: rajesh_thermal@yahoo.com (B. Rajesh Kumar), idhayapriyan@yahoo.co.in (S. Saravanan).
1
Tel.: þ91 4427152000; fax: þ91 4427162462.

http://dx.doi.org/10.1016/j.rser.2016.01.085
1364-0321/& 2016 Elsevier Ltd. All rights reserved.
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115 85

3.3. Use in low temperature combustion (LTC) applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

3.3.1. Combustion, performance and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.3.2. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.3.3. Future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.4. Butanol Dual-fuel injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.4.1. Combustion, performance and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.4.2. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.4.3. Future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.5. Neat butanol operation in diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.5.1. Combustion, performance and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
3.5.2. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.5.3. Future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4. Pentanol in diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4.1. Combustion, performance and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.2. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.3. Future research directions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5. Other higher alcohols in diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.1. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.2. Future research directions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

1. Introduction dual-injection, alcohol–diesel blends and alcohol–diesel emulsions

Diesel engines are indispensable equipment in public trans-
portation, heavy-duty machinery, power generation, agricultural
and industrial equipment owing to their higher fuel-conversion
efficiency, higher power output, higher torque capacity, higher
durability and higher reliability than gasoline engines. Moreover
they emit lesser carbon monoxide (CO), hydrocarbons (HC) and
carbon dioxide (CO2) emissions than gasoline engines. The use of
fossil diesel in diesel engines produces high NOx (nitrogen oxides)
and soot emissions that are detrimental to both environmental
and human health. Diesel exhaust is classified as carcinogenic to
humans by the International agency for research on cancer (IARC)
based on sufficient evidence that its exposure is associated with an
increased risk of lung cancer [1]. While soot emissions can cause
cardiovascular diseases [2], NOx present in diesel exhaust is a chief
cause for smog [3], ground level ozone [4], acid rain [5] and sick
building syndrome [6].
Growing concerns of fossil fuel depletion, oil-price fluctuations,
escalating energy demands and stringent emission regulations are
driving the scientific community to find alternative renewable
biofuels for use in diesel engines. Among the biofuels like bio-gas,
bio-alcohol and bio-diesel, alcohol seems to be most attractive.
Biogas requires high pressure for its use in automobile and its
leakage can be hazardous. Biodiesel from edible vegetable oil can
cause shortage in food supply. Non-edible oil sources require large
scale cultivation which can take up the land resources meant for
food crops. Alcohols can be obtained by anaerobic fermentation of
ligno-cellulosic biomass which includes agricultural waste bio-
mass (rice straw, corn stalks and sugarcane bagasse), forestry
biomass (wood-pulp, saw-mill and paper-mill discards) without
much reliance on food crops [7]. Further energy crops like switch
grass (Panicum virgatum) and elephant grass can produce high
yield of ligno-cellulosic biomass than can serve as raw materials
for alcohol production. Hence, availability of alcohols would not be
an issue.
Nevertheless, the use of lower alcohols like methanol and ethanol
in compression-ignition engines presents certain complications due
to their low cetane number, high latent heat of vaporization and high
resistance to auto-ignition [8]. Further the less calorific value, poor
miscibility with diesel and poor lubricating properties restricts their
use in diesel engines [9]. Several techniques like alcohol fumigation,
have been used to deal with these limitations of the alcohols as a
diesel engine fuel [10]. From the safety perspective, lower alcohols
have low flash point (FP) and are classified as Class I liquids (FP below
37.8 °C) along with gasoline by the National Fire Protection Associa-
tion (NFPA) in the US. Meanwhile, diesel fuel is classified under Class
II liquids (FP above 37.8 °C). But addition of lower alcohols to diesel
lowers the flash point and would make the blend to fall under Class I
liquids, consequently requiring the same infrastructure as gasoline
for storage and handling. On the other hand, there are some positive
aspects of alcohols that can be advantageous in diesel engines. The
reduction of smoke is strongly related to the oxygen-content of the
blends [11]. Alcohols being oxygenated fuels with a hydroxyl (OH)
group, increase the availability of oxygen during combustion and
reduce smoke emissions in diesel engines especially at high engine
loads [12]. With respect to the chemical structure, it is asserted that
smoke reduction efficiency is high in alcohol and low in ether [13].
Recently higher alcohols have gathered interest among the
researchers owing to their higher energy density, higher cetane
number, better blend stability and less hygroscopic nature when
compared to other widely-studied lower alcohols like ethanol,
methanol. Increase in length of the carbon chains also improves
the ignition quality of alcohol molecules [14]. The term ‘higher
alcohol’ usually refers to the series of straight chain alcohols
containing four or more carbon atoms, viz. butanol (C4), pentanol
(C5), hexanol (C6), octanol (C8), dodecanol (C12), phytol (C20) etc.
However propanol (C3) is also included in this study, as this three-
carbon alcohol is used as a solvent to bind lower alcohols with
diesel and also as a blending component with diesel fuel in diesel
engine. Table 1 presents a comparison of physical and chemical
properties of some lower and higher alcohols with diesel. It can be
inferred from the table that higher alcohols (when compared to
lower alcohols like methanol and ethanol) have greater potentials
to replace fossil diesel wholly or partially. Higher alcohols can mix
with diesel without any phase separation which is attributed to
their high carbon content, low polarity and less hygroscopic nature
[15,16]. Therefore no co-solvents or emulsifying agents would be
required to maintain blend stability when higher alcohols are
used. The increase in length of carbon chain and the absence of
branches in an alcohol provides high calorific value, density and
cetane number while conserving self-igniting characteristics and
less tendency to knock [15]. Higher alcohols have less corrosive
86 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115

action on materials used in the fuel delivery and injection systems
[17]. Higher the water content in the alcohols, higher the corrosive
action is. Higher alcohols are less hygroscopic and therefore can be
less corrosive. Moreover alcohols with high molecular weights are
known to be less corrosive [18]. Flash points of higher alcohols are
quite high which makes them safer to store, handle and deliver in
the existing distribution infrastructure. The lower vapor pressures
of higher alcohols also results in lower evaporative emissions [19].
Though longer chain alcohols have less oxygen content, they can
still enhance the premixed combustion phase with their relatively
longer ignition delay allowing sufficient mixing of air/fuel and also
improve the diffusion combustion phase. Furthermore, alcohols
with longer carbon chains consume lesser energy during its pro-
duction when compared to other lower alcohols since the biolo-
gical process of breaking down large macromolecules can stop
earlier [9].
The use of higher alcohols was earlier deterred by high pro-
duction costs, prolific use in food industry and limited production
from non-petroleum resources [20]. The last decade has witnessed
a renewed interest in higher alcohols (as sustainable vehicle fuels)
which reinvigorated many research groups and bio-technology
companies to increase the yield of higher alcohols like butanol and
pentanol from cellulose by modern fermentation processes using
new strains of Clostridium species [21] and by biosynthesis from
glucose using genetically engineered micro-organisms like
Escherichia coli [22], Cyanobacteria [23] and Saccharomyces cere-
visiae [24]. There is also an alternative route in which biomass can
be gasified or steam-reformed or partially oxidized to produce
synthesis-gas (CO, H2 and CO2) which can be catalytically con-
verted into higher alcohols by a process called Higher-alcohol
synthesis (HAS) [25].
Higher alcohols can also be produced by direct electro-
microbial conversion or photosynthetic recycling of carbon-
dioxide [26]. This method can indeed help recycling CO2 (a
greenhouse gas) into higher alcohols without the necessity to
deconstruct biomass [27]. Further, proprietary biochemical path-
ways for large scale commercial production of higher alcohols are
being developed by bio-fuel producers in-order to reduce the high
costs involved like Gevo [28,29] and Butamax [30]. The U.S.
Renewable Fuel Standard (RFS) program requires blending of
advanced biofuels in increasing amounts with fossil transportation
fuel every year which should escalate upto 36 billion gallons by
2022 [31]. According to this program, each renewable fuel cate-
gory should produce lower greenhouse gas emissions compared to
fossil gasoline or diesel it replaces. In this context, higher alcohols
can be used to meet these targets as they qualify as advanced
biofuels that can be derived from ligno-cellulose.
The main objective of this study is to provide a comprehensive
review of literature related to the use of higher alcohols in diesel
engines and their effects on the combustion, performance and
emissions of diesel engines. Many scientists and investigators have
studied the use of higher alcohols ranging from 3-carbon propanol
to 20-carbon phytol in various proportions with diesel to assess
their suitability as a fuel in the existing CI engines. The on-going
investigations and the previous findings about the replacement
(whole or partial) of fossil diesel fuel with higher alcohols in diesel
engines were found to be generally successful because they
reduced regulated emissions with improved efficiency besides
increasing the renewable fraction in the fuel.
2. Propanol in diesel engines
Propanol is a 3-carbon structure, straight chain alcohol with
higher energy density and higher cetane number which makes it a
potential alternative to lighter alcohols (methanol and ethanol) as
blending component with diesel. Propanol is primarily produced
from petrochemicals by oxo-synthesis which is currently the most
cost-effective process [32]. Due to concerns of depleting fossil
reserves, several sustainable pathways have been developed to
produce this alcohol. Propanol can be produced from feedstocks
such as biomass or municipal solid waste. These feedstocks are
gasified into syngas (CO, H2 and CO2) and then converted into
biofuels using microbial catalysts such as Clostridium ljungdahlii
and Clostridium ragsdalei [33]. However, microbial production of
propanol from Clostridium species via, threonine catabolism or
from yeast in beer fermentation yielded only very small quantities
of less than 70 mg/L [34]. There is also no existing micro-organism
that can naturally produce propanol from glucose in substantial
quantities. Therefore, researchers have turned to bio-synthetic
pathways to produce industry-relevant quantities of propanol
from Escherichia coli, a microorganism that can be easily
manipulated than the traditional complex Clostridium species
[34,35]. Recently several biochemical, genetic, and metabolic
engineering strategies are being devised to enhance the co-
production of 1-propanol and ethanol from a novel engineered
Escherichia coli [36].

Table 1
Propertiesa of higher alcohols in comparison with diesel and other lower alcohols.

Properties Diesel Methanol Ethanol Propanol Butanol Pentanol Hexanol Octanol Decanol Phytol

Molecular formula CXHY CH3–OH C2H5–OH C3H7–OH C4H9–OH C5H11–OH C6H13–OH C8H17–OH C9H19–OH C20H39–OH
Molecular weight (Kg/kmol) 190–211.7 32.04 46.07 60.09 74.12 88.15 102.18 130.23 158.28 296
C (%wt) 86.13 37.48 52.14 59.96 64.82 68.13 70.52 73.72 68.23 81.08
H (%wt) 13.87 12.48 13.02 13.31 13.49 13.61 13.70 13.82 12.64 13.51
O (%wt) 0 49.93 34.73 26.62 21.59 18.15 15.70 12.29 10.11 5.4
Solubility (g/L) Immiscible Miscible Miscible Miscible 77 22 7.9 4.6 3.7 –
Lubricity (μm corrected wear scar) 315 1100 1057 922 591 670.5 534 404 406 –
Cetane number 52 5 8 12 17 18.2–20 23 39 50 45.9
Self-ignition temperature (°C) 254–300 463 420 350 345 300 285 270 255 –
Density (kg/m3) at 15°C 835 791.3 789.4 803.7 809.7 814.8 821.8 827 830 850.9
Viscosity at 40 °C (mm/s2) 2.72 0.58 1.13 1.74 2.22 2.89 5.32  6.5 63.54
Lower heating value (MJ/Kg) 42.49 19.58 26.83 30.63 33.09 34.65 39.10 52.94  43.6
Latent heat of evaporation (kJ/kg) 270–375 1162.64 918.42 727.88 581.4 308.05 486   
Vapor pressure (mmHg) 0.4 127 55 20 7 6 1 0.08 o 0.1 
CFPP b (°C)  17 o  51 o  51 o  51 o  51  40 – – – –
Boiling point (°C) 180–360 64.7 78.3 97.1 117.5 137.9 157 195 233 204
Flash point (°C) 455 11–12 17 11.7 35–37 49 59 81 108 –

a
Data taken from Refs. [12,15,186–189];
b
CFPP – Cold filter plugging point.
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
Very few detailed experimental and kinetic modeling studies
regarding the combustion chemistry of n-propanol and iso-pro-
panol have been carried out when compared to ethanol and
methanol [37–40]. It was recently found that among the 3-carbon
fuels (propane, n-propanol, propanal and acetone), propanal
showed highest flame speeds while n-propanol and propane
presented comparable laminar flame speeds and similar radical
concentrations, especially H and OH [41]. Apart from providing
deeper insights into the fundamentals of propanol combustion,
these studies also impart information regarding the toxic oxyge-
nated pollutants (like aldehydes and acetones) that are common
byproducts of alcohol combustion [37]. It was found that the main
aldehydes produced during oxidation of propanol were for-
maldehyde and propanaldehyde. Ethylene, methane, and propene
were the other main intermediate hydrocarbons formed [39].
Propanol is either used as a blending component with diesel or
as a diluting agent to reduce viscosity in vegetable oil-fueled diesel
engines. All propanol/diesel blends are found to be stable above
2.5 °C. Blends with propanol content above 45% v/v do not fulfill
the kinematic viscosity requirement as per European diesel quality
norm EN 590. Blends that contain high volumes of propanol
(4 80% v/v) do not satisfy the lubricity requirements of EN 590
which is a corrected wear scar below 460 μm at 60 °C [12].
2.1. Combustion, performance and emission characteristics
There are very few studies that reported propanol usage in
diesel engines. Table 2 provides a summary of investigations that
studied the performance and emission characteristics of various
diesel engines fueled with propanol/diesel blends.
Laza et al. [42] examined the influence of adding propanol (10%
and 20% v/v) with rapeseed oil in a single cylinder, four-stroke CFR
(Cooperative Fuel Research) engine. Propanol reduced the smoke
emissions of rapeseed oil but increased NOx, total hydrocarbons
(THC) and CO emissions significantly. In a similar study [43],
propanol was mixed upto 20% v/v with neem oil and was tested in
a single cylinder diesel engine under different loads at a constant
speed of 1500 rpm. Addition of propanol improved the perfor-
mance of the engine with considerable reductions in regulated
emissions when compared to neat neem oil operation. Recently,
Mishra et al. [44] conducted an experimental study to evaluate the
use of propanol as a supplement to callophyllum vegetable oil at
different blend ratios (10%, 20% and 30% v/v) in a single-cylinder,
direct injection (DI) diesel engine working at a speed of 1500 rpm
under six different loads. A drop in peak pressure and a slight
increase in ignition delay were observed with increasing propanol
content in the oil. There are significant reductions in smoke den-
sity, CO and HC emissions but NOx emissions increased with the
use of propanol-callophyllum vegetable oil blends compared to
neat diesel operation.
Banugopan et al. [45] used 1% iso-propanol as an additive for
improving the homogeneity and phase stability in ethanol–diesel
blend fuels. Yoshimoto et al. [46] found that addition of n-propa-
nol to rapeseed oil produced stable combustion and resulted in
low smoke emissions with unchanged NOx emissions and slight
penalty in brake specific energy consumption (BSEC). In a similar
study, Yoshimoto et al. [47] obtained completely miscible mixtures
with 29% n-propanol and rapeseed oil. The performance and
emission trends were found to be similar to that of their
previous study.
An experimental study for analyzing the performance and
emissions in a single cylinder, constant speed diesel engine was
executed by Chockalingam et al. [48] using four ternary blends of
diesel, methanol and propanol in varied proportions. An improved
performance was noted with these blends and the blend con-
taining 60% diesel, 20% methanol and 20% propanol delivered an
87
efficiency of 35.92% against 30.6% obtained from neat diesel. While
NOx and smoke emissions weren’t affected, there was a drastic
increase in HC emissions when the methanol content of the blend
increased beyond 20%.
Propanol/diesel blends (5%, 10%, 15% and 20% v/v) were repor-
ted to decrease NOx emissions significantly when compared to
diesel fuel in an unmodified single cylinder diesel engine. The use
of 15% and 20% blends also increased brake thermal efficiency
(BTE) slightly. HC emissions increased with increasing propanol
content in the blends. Smoke opacity is lower for 20% blend at
peak loads with insignificant variation in BSFC of the engine [49].
In another investigation, a diesel engine operated at constant
speed was fueled with neat diesel fuel, 4% and 8% propanol-diesel
blends. The addition of 8% propanol to diesel fuel increased BTE by
upto 7.635% at medium and high loads. Smoke and NOx emissions
decreased and HC emissions increased with increasing propanol
content in the blends [50]. Recently, Hazar et al. [51] studied the
effects of 2%, 8%, 12% and 16% propanol-diesel blends in a three-
cylinder DI diesel engine and found that NOx emissions increased
while smoke density, CO and HC emissions decreased in compar-
ison with neat diesel operation.
2.2. Summary
There is conclusive evidence from the literature that propanol
can be mixed with diesel without any phase separation upto 20%
v/v. In similar lines, propanol can also be mixed with vegetable oils
without a need of an emulsifying agent upto 30% v/v. Taken
together, the results of the referenced studies indicate that
propanol-addition to diesel leads to the following effects on per-
formance and emission of a diesel engine in comparison with neat
diesel operation,
 There is a slight increase in ignition delay due to lower cetane
number of propanol.
 There is an improvement in performance of the engine which is
attributed to the higher percentage of premixed combustion as
a result of low cetane number of propanol and improved spray
characteristics due to decrease in viscosity and density of the
blends.
 Soot emissions generally decreased with increasing propanol
content in the blend due to its oxygenated nature. The lower
carbon content of propanol is also a reason behind this
reduction.
 NOx emissions generally decreased with increasing propanol
content in the blend. This is due to the dominance of tem-
perature lowering effect of alcohols as result of its higher heat of
vaporization over the possible higher temperatures during the
premixed combustion phase as a result of longer ignition delay
(due to its lower cetane number). This is a delicate balancing
which can weigh more on the either side depending on the
specific engine and its operating conditions [52]. This is the
reason behind the contrasting trend in NOx emissions in this
particular study of Hazar et al. [51].
 HC emissions presented an increasing trend with increasing alco-
hol content in the blend. This is due to the high latent heat of
vaporization of alcohol which causes slow evaporation, incomplete
air/fuel mixing, a development of a quench layer [51].
 CO emissions generally decreased with propanol content espe-
cially at high load due to the high in-cylinder temperature
prevailing at that condition.
Addition of propanol to vegetable oil results in the following
effects on performance and emission of diesel engine when
compared to its neat vegetable oil operation,
 88
Table 2
Summary of investigations that used propanol in diesel engines.

Ref Engine Fuel Test conditions Reference fuel Blend Performance NOx Soot HC CO
Designation

[42] 1-cylinder, 4S, IDI, CFR (Coop- Rapeseed Oil (RPO) Constant speed. Rapeseed oil RPO100 PP ▼ ▼ ▼ ▲ ▲
erative Fuel Research) Engine Rapeseed Oil (RPO) þ RPO90-PR10
10% Propanol (PR) RPO80-PR20
Rapeseed Oil (RPO) þ
20% Propanol (PR)

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
[43] KIRLOSKAR TV1 Neem Oil (NO) Variable loads, Neem oil NO100 BTE highest for diesel. ▼ ▼ ▲ low loads ▲ low loads
1-cylinder, 4S, RP: 4.4KW, CR: Neem Oil (NO)þ 1500 rpm. NO95-E5 BTE ▲ with increase ▼ high loads ▼ high loads
16.5:1, WC, DI diesel engine Ethanol (E) NO90-E10 in alcohol content
Neem Oil (NO)þ NO95-PR5 BSEC ▼ with increase
Propanol (PR) NO90-PR10 in alcohol content
Neem Oil (NO)þ NO85-PR15
Butanol (B) NO80-PR20
Neem Oil (NO)þ NO95-B5
Pentanol (P) NO90-B10
NO85-B15
NO80-B20
NO95-P5
NO90-P10
NO85-P15
NO80-P20
[44] KIRLOSKAR Calophyllum Vege- Variable loads. Diesel CVO90-PR10 PP ▼ ▼ ▼ ▼ ▼
1-cylinder, 4S, RP:3.5KW, table oil (CVO)þ CVO80-PR20 ID ▲
CR:17.5:1, DI diesel engine Propanol (PR) CVO70-PR30
[48] KIRLOSKAR Diesel (D) þ Variable loads, Diesel D80-M10- ▲ 3 3 ▲ n/a
1-cylinder, 4S, RP:5.2KW, AC, Methanol (M) þ 1500 rpm. PR10
DI diesel engine Propanol (PR) D70-M20-
PR10
D60-M20-
PR20
D50-M30-
PR20
[49] KIRLOSKAR Diesel (D) þ Variable loads, Diesel D95-PR5 BTE PR5 ▼ PR20 ▼ ▲ ▼ high loads
1-cylinder, 4S, DI diesel engine Propanol (PR) D90-PR10 PR15 ▲ 5.8% high loads
D85-PR15 PR20 ▲ PR20
D80-PR20 BSFC ▼ 13.4%
▲ low loads
3 high loads
[50] KIRSOLSKAR Diesel (D) þ Variable loads, Diesel D92-PR8D96- BTE ▼ with alco- ▼ with alcohol ▲ with alcohol ▼ with alcohol
1- cylinder, 4S, RP:5.2KW, Propanol (PR) 1500 rpm. PR4 ▲ 1.579% for PR4 hol content content content content
CR:17.5:1, WC, DI diesel engine ▲ 7.635% for PR8
at medium and
high loads
[51] INTER-IDE314NG Diesel (D) þ Variable loads, Diesel D98-PR2 n/a ▲ with alco- ▼ with alcohol ▼ with alcohol ▼ with alcohol
3-cylinder, 4S, RP:13.5KW, Propanol (PR) 1500 rpm. D92-PR8 hol content content content content
CR:18:1, WC, DI diesel engine. D88-PR12
D84-PR16

▲ - increases; ▼ - decreases; 3 - no change; 4S – Four stroke; DI – Direct injection; IDI – Indirect injection; RP – Rated power; CR – Compression ratio; AC – Air-cooled; WC – Watercooled; BTE – Brake thermal efficiency; BSFC –
Brake specific fuel consumption; PP – Peak pressure; ID – Ignition delay; n/a – not available.
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
 Ignition delay increases with increasing propanol content in
vegetable oil. This is due to the lower cetane number of propanol.
 The performance of the engine is better due to the improved
atomization and spray characteristics as propanol addition
resulted in lower kinematic viscosity and density of vegetable
oil. The lower cetane number of propanol also resulted in higher
percentage of constant volume combustion which in-turn
increased the efficiency of the engine.
 The higher heat of vaporization of propanol lowered the com-
bustion temperature. This in-turn causes a reduction in
temperature-dependent NOx emissions.
 Smoke emissions of neat vegetable oil operation are usually
higher than diesel fuel. Addition of propanol decreases the
smoke emissions due to the improved oxygen availability.
 From the few available literature, the evidence regarding the
effect of propanol addition to vegetable oil on HC and CO
emissions is inadequate to draw any firm conclusions. This may
due to the variation in properties of the vegetable oil used in
these studies.
2.3. Future research directions
 Further studies are required to explore the feasibility of using
propanol/diesel blends higher than 20% by using cetane number
(CN) improvers like 2-ethyl hexanitrate, diglyme or diethyl
ether etc.
 There are currently no studies that attempted dual-fuel opera-
tion of propanol in diesel engines. The possibility of propanol
fumigation in the intake port and auto-igniting the mixture by
diesel could be attempted.
 Propanol has low reactivity, high volatility and long ignition
delay. These properties make propanol a potential candidate to
enable LTC or Homogenous charge compression ignition (HCCI)
operation in diesel engines and could be possibly explored.
 Propanol/vegetable-oil/diesel and propanol/biodiesel/diesel
ternary blends will have higher cetane numbers and high oxy-
gen content. The feasibility of these ternary blends in diesel
engines should be explored.
3. Butanol in diesel engines
n-butanol often referred to as ‘butanol’, is a 4-carbon straight
chain alcohol that can be produced from biomass (bio-butanol) as
well as fossil fuels (petro-butanol). Nevertheless both have same
chemical properties and produce similar effects when used in
engines. Biofuels have grabbed the attention of engine researchers
ever since the oil crisis and the rising costs of petrochemicals
cropped up in the ‘70 s. Ethanol was the most focused alcohol at
that time because the popular yeast fermentation process pro-
duced 2.5 gallons of ethanol whereas the ABE (acetone–butanol–
ethanol) fermentation process managed only 1.3 gallons of butanol
from a bushel of corn [53]. However, these days the use of modern
fermentation processes has improved the yield of butanol con-
siderably. The last decade has witnessed a significant amount of
research in developing butanol production technologies with the
use of genetically modified strains of Clostridium and Escherichia
coli, gas stripping, ionic liquids, pervaporation and supercritical
extraction [10,54–56]. The current fermentation processes for
ethanol production have a maximum carbon conversion yield of
67 percent. Recently, a new biobutanol technology known as
Butyfix process was introduced by Taiwan's Industrial Technology
Research Institute (ITRI) that can convert 94 percent of the avail-
able carbon in biomass [57]. Some key features of butanol bio-
production and utilization with respect to ethanol are as follows:
89
 Butanol can be produced from the same biomass feedstocks
used for ethanol production like wheat, corn, sugar beet, corn,
sugarcane and cassava.
 Butanol can be produced from both five and six carbon sugars
without organism modification [58].
 Existing ethanol plants can be retro-fitted to produce butanol
and existing pipelines can be used to transport butanol [59].
 Butanol require less energy for its production as the process of
breaking down the complex macromolecules to lower mole-
cules can stop earlier and save energy [9].
 The federal Renewable fuel standard (RFS) requires 36 billion
gallons of renewable fuel which includes 21 billion gallons of
advanced biofuels to be used by 2022. Refiners and blenders
were obligated to submit credits in the form of Renewable
identification number (RIN) which corresponds to the each
gallon used. Butanol can generate twice the number of RINs
than ethanol without exceeding the blend wall. In other words,
10% of ethanol (E10) will generate only 10 RINs while 16.1% of
butanol can produce 20.93 RINs, without exceeding 3.5% by
weight of oxygen in a blend [60].
 Butanol can also be used in the esterification of vegetable oils to
biodiesel like ethanol [53].
Year-round production of butanol (at an average of 0.11 g of
butanol/g of sugar) can be ensured from carbohydrates and
lipids obtained through algae that can be grown and harvested
from partially treated sewage water [61]. The potential use of
duckweed as a next-generation biomass feedstock was recently
explored. Duckweed is a fast-growing floating aquatic species
that can produce maximum biomass yield at low costs in
minimum time. A novel bio-engineered micro-organism Cory-
nebacterium crenatum was used to ferment this biomass and
produce high iso-butanol yield [62].
Several studies have investigated the combustion characteristics
and soot distributions of neat-butanol, n-butanol/diesel blends
in comparison with other biofuels under different ambient
temperatures and oxygen conditions in a constant volume
combustion chamber [63–68]. High speed imaging, time-
resolved images of spray and natural flame luminosity were
used. Liu et al. [63] affirmed that n-butanol had a higher
normalized peak pressure compared with biodiesel which
suggests that butanol potentially has higher thermal efficiency.
Further, n-butanol is more effective in suppressing the soot
formation and shows stronger soot reduction capability than
that of biodiesel [66].
Though butanol is not suitable for directly replacing diesel in CI
engines, its properties as seen from Table 1 indicates that it can
be added in significant amounts to diesel fuel and used. The
following points present a summary on why butanol is a
potential candidate for use in diesel engines.
 Butanol is hydrophobic, in other words, it repels water and
provide good inter-solubility with diesel without phase
separation.
 The cetane number of butanol is reported to be as high as 25
which is better than lower alcohols to help auto-ignition [58].
 High calorific value of butanol implies 25% extra energy when
compared to ethanol.
 Stoichiometric air/fuel ratio of butanol is closer to diesel fuel [8].
 Lower volatility of butanol prevents cavitation and vapor lock
problems [53].
 Butanol is less corrosive and can be stored in normal tanks for a
longer duration.
 High flash point of butanol ensures safe transportation and
handling.
 High viscosity reduces wearing of moving parts in fuel systems
and engine.
The following methods are employed to enable the use of
90 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115

Table 3
a
Properties of butanol isomers.

Properties Diesel n-Butanol sec-Butanol iso-Butanol tert-Butanol

Molecular structure –

Molecular weight (Kg/kmol) 190–211.7 74.12 74.12 74.12 74.12

C (%wt) 86.13 64.82 64.82 64.82 64.82
H (%wt) 13.87 13.60 13.60 13.60 13.60
O (%wt) 0 21.59 21.59 21.59 21.59
Cetane number 52 17 – – –
Self-ignition temperature (°C) 254–300 345 406.1 415.6 477.8
Density (kg/m3) at 15°C 835 809.7 806 802 789
Lower heating value (MJ/Kg) 42.49 33.09 32.74 33.11 29.79
Latent heat of evaporation (kJ/kg) 270–375 581.4 671 684 511
Vapor pressure (mm/Hg) – 7.2 12.5 8.0 30.1
Boiling point (°C) 180–360 117.5 99.5 108 82.4

a
Data taken from Ref. [77].

butanol in diesel engines and will be focused in the current
review:
 Direct blending of butanol with diesel to form a stable
binary blend.
 Dual-fuel injection, ie. Port fuel injection of butanol into the
intake air and auto-ignition using direct injection of diesel or
biodiesel.
 Using in its neat form by Port fuel injection (PFI) or direct high
pressure injection.
The use of butanol with vegetable oil or biodiesel as binary and
ternary blends with diesel in diesel engines is not included in this
study. The vast amount of literature in this area required it to be
covered in a separate review that will be carried out by the
authors in the near future.
3.1. Comparative behavior of butanol isomers in diesel engines
There are four isomers of butanol based on the location of
hydroxyl group and the carbon chain structure which are,
(i) n-butanol–CH3–CH2–CH2–CH2–OH–straight chain alcohol with
hydroxyl group at terminal carbon,
(ii) sec-butanol–CH3–CH2–CH–OH–CH3–straight chain alcohol with
hydroxyl group at internal carbon,
(iii) iso-butanol–(CH3)2–CH2–CH–OH–branched chain alcohol with
hydroxyl group at terminal carbon and
(iv) ter-butanol–(CH3)3–C–OH–branched chain alcohol with hydroxyl
group at internal carbon.
The production methods of all isomers are different. Biological
pathways exist for the production of the first three isomers except
for ter-butanol which is derived from petrochemicals [69,70]. All
isomers have same molecular weight but different molecular
structures that affects their properties. The properties of all iso-
mers are presented in Table 3. They have similar energy content
but have different physical properties including solubility, density,
latent heat of vaporization and boiling point. Hence their behavior
in diesel engines could also be different. While n-butanol, sec-
butanol and iso-butanol are immiscible in water, ter-butanol is
soluble in water [71].
Many experimental and kinetic modeling studies on combus-
tion of four isomers of butanol were carried out by many
researchers [70–73]. Moss et al. [71] measured the ignition delay
times for n-butanol, sec-butanol, iso-butanol and ter-butanol for a
common mixture composition and pressure and showed that
ignition times vary from longest to shortest (least reactive to most
reactive) in the order of ter-butanol, sec-butanol, iso-butanol, and
n-butanol. Grana et al. [72] found that the flame structures and
overall combustion characteristics of all four isomers are similar.
The high temperature auto-ignition of these four isomers in a
shock-tube at atmospheric pressure revealed that n-butanol is the
most reactive and ter-butanol is the least reactive among the
isomers. Gu et al. [74] measured the laminar burning velocities of
butanol isomer–air mixtures at various initial pressures. It was
found that branching and position of OH-group affect the laminar
burning velocities which are in the order of n-butanol 4 sec-
butanol4 iso-butanol 4ter-butanol.
Later Gu et al. [75] examined the consequences of using n-
butanol/diesel and iso-butanol/diesel blends on diesel engine
performance and emissions. The results showed that iso-butanol/
diesel blends produced higher peak cylinder pressure and higher
premixed heat release rate than n-butanol/diesel blends. CO
emissions are higher for iso-butanol/diesel blends when compared
to n-butanol/diesel blends. This is attributed to lower combustion
temperatures of iso-butanol than n-butanol. This work clearly
demonstrated that different butanol isomers exhibit different
combustion and emission characteristics in diesel engines.
In a study that compared and evaluated the effects of adding
20% v/v of n-butanol and sec-butanol to diesel fuel on combustion
and emissions of a diesel engine operating over a wide range of
EGR encompassing both conventional diesel combustion (CDC)
and LTC, Liu et al. [76] showed that the combustion characteristics
of both n-butanol/diesel and sec-butanol/diesel were very similar
and the soot emissions of n-butanol/diesel blend were slightly
higher than those of sec-butanol/diesel blend. Eventually it was
demonstrated that soot emissions were slightly impacted by the
position of the hydroxyl radical between n-butanol and sec-
butanol.
Recently, Zheng et al. [77] conducted an experimental study
that presented a new perspective on the molecular structures of
butanol isomers. This study evaluated and compared all four
butanol isomers as a supplement to conventional diesel fuel at two
different blend ratios (20% and 40% v/v) in a single cylinder, water-
cooled CRDI (common rail direct injection) diesel engine under a
wide range of EGR rates from 0% to  65%. The ignition delays of
four butanol-isomer/diesel blends, from longest to shortest are
found to be in the order of iso-butanol, sec-butanol, n-butanol and
ter-butanol. The sequence of combustion duration of four blends,
from longest to shortest is: ter-butanol, n-butanol, sec-butanol and
iso-butanol. Soot emissions of four blends, from highest to lowest
are: ter-butanol, n-butanol, sec-butanol and iso-butanol. The lower
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
soot emissions of sec-butanol/diesel blend when compared to n-
butanol/diesel blend is attributed to the fact that sec-butanol/
diesel blend has lower distillation temperature. All blends pre-
sented minor variations in thermal efficiencies.
3.2. Diesel/butanol blends
Diesel/butanol blends are one of the several possibilities that
can be utilized to make diesel technology compatible with alco-
hols. The hydrophilic nature of short-chain alcohols like ethanol
and methanol prevents them from forming a stable blend with
diesel. They separate into different liquid phases over a period of
time and if this happens inside a fuel tank, it causes undesirable
effects in the engine system. Hence a co-solvent is required to
achieve a better blend. But butanol as a consequence of its lower
polarity exhibits better miscibility characteristics with diesel [12].
Diesel/butanol blends require no emulsifying agents as they don’t
phase separate even after several days [78]. Interestingly, butanol
itself is used as a surfactant in methanol/diesel blends [79] and
ethanol/diesel blends [80–82]. The ease of attaining a stable diesel/
butanol blend also eliminates the necessity of a special production
facility to process it because mixing can be done either in-line at
the terminal or splash-blended in the storage tank just before
delivery [83]. Another notable advantage is that butanol can be
blended in higher proportions with diesel which implies higher
renewable fraction in the fuel. Several researches involving diesel/
butanol blends indicate that butanol can replace upto 40% of diesel
fuel without any major modifications in the existing engine
infrastructure [84].
The low heating value of a fuel represents the amount of
energy it releases when it is burnt completely. This property
affects the power output of the engine. The heating value of
alcohol increases with increase in number of carbon atoms which
indicates higher heating values for butanol than ethanol and
methanol. However, the heating value of butanol is 23% lower than
diesel and hence would require more amount of diesel/butanol
blends to produce the same power output in the engine. The
volatility and auto-ignition temperature of an alcohol decreases
with the increase in number of carbon atoms. Hence diesel/buta-
nol blends will not run into ignition problems at low load condi-
tions [85]. Viscosity and density are two crucial properties for
engine performance because it affects spray formation, spray
penetration, fuel droplet size, injection timing, injection pressure,
atomization and combustion characteristics. Addition of butanol to
diesel lowers its density and viscosity. Alcohols have high octane
number and low cetane number. This specific reason prevents
their direct usage in an unmodified compression ignition engine.
However when blended with diesel, butanol lowers the cetane
number of the blends which brings about deterioration of auto-
ignition characteristics and a longer ignition delay.
3.2.1. Combustion, performance and emission characteristics
This section presents a comprehensive review of investigations
that used butanol as a blending component with diesel (without
any additives or co-solvents) and its effects on combustion, per-
formance and emission characteristics in various diesel engines. A
summary is presented in Table 4.
One of the earliest investigations involving the use of butanol
in diesel engines was carried out by Miers et al. [86]. A drive-cycle
analysis was performed on a four cylinder turbocharged engine
using butanol/diesel blends (20% and 40%) and was found that fuel
consumption has increased with increase in butanol content in the
blends. A reduction of upto 80% filter smoke number was observed
with 40% blend during steady state tests whereas the same blend
decreased the drive-ability for the cold-start urban drive cycle.
While it was reported that NOx emissions were impacted during
91
the highway drive cycle, THC and CO emissions weren’t sig-
nificantly affected.
Al-hasan et al. [84] concluded that upto 30% iso-butanol addi-
tion would deliver better performance than diesel after investi-
gating four iso-butanol/diesel blends (10, 20, 30 and 40% v/v) in a
diesel engine. It was found that exhaust temperature and air-fuel
ratio decreased with increase in engine speed. However, this
research did not include emission characteristics. In this context,
Karabektas et al. [8] investigated the performance as well as
emissions of a single cylinder DI diesel engine using four iso-
butanol diesel blends (5%, 10%, 15% and 20% v/v) at full load con-
ditions at the speeds between 1200 and 2800 rpm. A slight
decrease in brake power was reported with blends upto 10% iso-
butanol while it still worsened for higher blends. At high engine
speeds, the 10% blend showed improved efficiency. NOx, CO
emissions decreased for all blends but HC emissions shot higher
compared to baseline diesel operation.
The first systematic study on butanol usage in diesel engine
was reported by Rakopoulos et al. [87] earlier to which, an open
literature that examined the effects of diesel/butanol blends on the
performance and emission of diesel engines was nearly absent.
This particular study used three diesel/butanol blends (8, 16 and
24% v/v) on a fully instrumented, single cylinder, high-speed, DI
diesel engine. It was revealed that smoke density, CO and NOx
emissions reduced linearly with butanol percentage in the blends.
As regards engine performance, BSFC and BTE slightly increased
with increase in butanol content in the fuel. A similar study was
conducted using two diesel/butanol blends (8 and 16%) by Rako-
poulos et al. [88] in a different engine which is a Mercedes-Benz,
six cylinder engine, DI diesel engine that powered the mini-bus
sub-fleet of Athens Transport. The findings regarding the perfor-
mance and emissions were comparable to those of the study
reported earlier [87]. In a related study, Rakopoulos et al. [78]
analyzed the combustion behavior of the same engine fueled with
similar blends. It was found that ignition delay prolonged and the
fuel injection pressure diagrams got displaced marginally. Peak
cylinder pressures came down slightly due to butanol addition
while the cylinder temperatures got lowered during early stages of
combustion and smoothened later. Both BSFC and BTE increased
with increase in butanol content in the blends whereas smoke and
NOx emissions decreased. There was no information on HC and CO
emissions in this investigation.
An experimental study was performed by Yao et al. [85] to
investigate the influence of n-butanol content (5, 10 and 15% v/v)
in a heavy-duty DI diesel engine with multi-injection capability.
EGR was adjusted to keep the NOx emissions constant. They found
that soot and CO emissions reduced significantly without affecting
the BSFC. Soot invariably decreased with all injection strategies
(Single, pilot-main, post, pilot-main-post) deployed. It was con-
cluded that a triple-injection strategy reduced soot emissions to
the maximum with the highest butanol fraction in diesel.
Dogan [19] examined the consequences of using butanol–diesel
fuel blends (5, 10, 15 and 20% v/v) in a small diesel engine at a
constant engine speed and different loads. The findings of this
research were consistent with the results of the previous findings
[78,87,88] and contributed to the understanding of improvement
of BTE despite the increase in BSFC. It was established that the
increase in BTE is due to the higher burner velocities of butanol
when compared to diesel. Further it was stated that the oxyge-
nated nature of butanol aids the diffusion combustion phase and
enhances the BTE.
An investigation regarding the effects of iso-butanol/diesel
blends (5, 10 and 15% v/v) on the performance, combustion and
emissions of a turbo charged, six cylinder, heavy duty, DI diesel
engine was executed by Ozsezen et al. [10]. Tests were conducted
at constant engine speed (1400 rpm) and three loads (150, 300
 92
Table 4
Summary of investigations that used butanol as a blending component with diesel fuel in various diesel engines.

Ref Engine Fuel Test conditions/variables Blend Reference fuel Performance NOx Soot HC CO
designation

[86] 4-cylinder, turbo- Diesel (D)þ Cold and hot start urban D80-B20 Diesel BSFC ▲ Urban ▼ Urban drive cycles Urban
charged, CRDI diesel Butanol (B) and highway drive D60-B40 drive cycles ▲ drive cycles
engine cycle tests. B20 3 Highway drive cycle ▲
35 mph and 55 mph B40 ▼ 3 Highway
steady-state test Highway drive drive cycle
cycle ▲ 3
[84] 1-cylinder, 4S, RP:6KW, Diesel (D)þ Variable loads, 375 to D90-IB10 Diesel BP ▼ n/a n/a n/a n/a
DI diesel engine. Iso-butanol (IB) 625 rpm. D80-IB20 BSFC ▲

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
D70-IB30 BTE ▼
D60-IB40 with increase in
butanol content.
[8] 1-cylinder, 4S, RP:14KW, Diesel (D)þ Full load, 1200 and D95-IB5 #2 Diesel BP ▲ with IB5 4.9 to 13.9% with n/a ▲ 12.9 to 32.9% with all ▼ 3.2 to 11.3%
CR:17:1, WC, DI diesel Iso-butanol (IB) 2800 rpm. D90-IB10 BP ▼ 1.47 to 6.04% all blends. blends with all
engine D85-IB15 with IB10 to IB20 average loads blends
D80-IB20 blends.
BSFC ▲ 2.06 to
8.55% with IB5 to
IB20 blends.
BTE ▲ for IB5 and
IB10 blends at
high speeds.
BTE ▼ for IB15
and IB20 at all
speeds.
[87] 1-cylinder, 4S, CR:19.8:1, Diesel (D)þ Low, medium and high D92-B8 Diesel BSFC ▲ with ▼ with increase in ▼ with increase in ▲ with increase in ▼ with
WC, HS, DI diesel engine Butanol (B) loads, 2000 rpm, Static D84-B16 increase in butanol butanol butanol increase in
injection timing D76-B24 butanol. butanol
BTE ▲ with
increase in
butanol.
[88] 6-cylinder, 4S RP:177KW, Diesel (D)þ Variable loads, 1200 and D92-B8 Diesel BSFC ▲ with ▼ with increase in ▼ with increase in ▲ with increase in ▼ with
CR:18:1, WC, turbo- Butanol (B) 1500 rpm D84-B16 increase in butanol butanol butanol increase in
charged, HD, DI diesel butanol. butanol
engine BTE ▲ with
increase in
butanol.
[78] 6-cylinder, 4S RP:177KW, Diesel (D)þ Variable loads, 1200 and D92-B8 Diesel BTE ▲ with ▼ with increase in ▼ with increase in n/a n/a
CR:18:1, WC, turbo- Butanol (B) 1500 rpm D84-B16 increase in butanol butanol
charged, HD, DI diesel butanol.
engine BSFC ▲ with
increase in
butanol.
ID ▲
PP ▼
[85] 6-cylinder, WC, CR:16:1, Diesel (D) BMEP 1.16MPa, 1840rpm, D95-B5 Diesel BSFC No serious 3 ▼ n/a ▼
turbo-charged, inter- þButanol (B) NOx maintained at 2.0 g/ D90-B10 impact.
cooled, heavy-duty, CRDI kWh using EGR. D85-B15
diesel engine Multiple injection
strategies.
[19] 1-cylinder, 4S, CR:18:1, Diesel (D)þ Variable loads, 2600 rpm. D95-B5 Diesel BSFC ▲ with ▼ with increase in ▼ with increase in ▲ with increase in ▼ with
AC, naturally aspirated, Butanol (B) D90-B10 increase in butanol butanol butanol increase in
HS, DI diesel engine D85-B15 butanol. butanol
D80-B20
 BTE ▲ with
increase in
butanol.
[10] 6-cylinder, 4S, Diesel (D)þ Variable loads, 1400 rpm D95-IB5 LSD BSFC ▲ with ▼ with increase in ▼ with increase in 1.5% IB5 ▼ with
RP:163KW, CR:16.4:1, Iso-butanol (IB) D90-IB10 increase in butanol butanol 1% IB10 increase in
WC, turbo-charged, HD, D85-IB15 butanol. ▲ 2.5% IB15 butanol
DI diesel engine. BTE ▼ with
increase in
butanol.
[112] 1-cylinder, 2S, CR:10.1:1, Diesel (D)þ Buta- Injection timings, EGR D80-B20 Diesel BSFC 3 ▼ with increase in ▼ with increase in n/a n/a
CRDI diesel engine nol (B) rates. ID ▲ butanol butanol
[110] 4-cylinder, turbo- Diesel (D)þ BMEP 0.5 MPa, D60-B40 LSD ID ▲ ▼ ▼ ▲ ▲
charged, CR:17.5:1, WC, Butanol (B) 2000 rpm. D60-G40 for both blends
CRDI diesel engine Diesel (D)þ BMEP 0.8 MPa, BTE

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
Gasoline (G) 2500 rpm. B404G40
[109] 4-cylinder, turbo- Diesel (D)þ Buta- BMEP 0.8 MPa, 2500 rpm, D80-B20 LSD ID ▲ ▼ ▼ ▲ n/a
charged, CR:17.5:1, WC, nol (B) Injection timing, EGR rate, D60-B40 BSFC ▼ 5–7%
CRDI diesel engine Injection pressure
[91] 4-cylinder, 4S, turbo- Diesel (D)þ Cold and warm D90-B16 LSD n/a During cold During cold start, ▲ During cold start, ▲ During cold
charged, inter-cooled, Butanol (B) starting. D84-E10 start, ▲ During warm During warm start, ▼ start, ▲
CRDI diesel engine Diesel (D) þ During warm start, ▼ During warm
equipped with cooled Ethanol (E) start, ▼ start, ▼
EGR, DOC and regen-
erative wall-flow type
DPF.
[89] 1-cylinder, 4S, WC, CRDI Diesel (D)þ Buta- 1400 rpm, Diesel injection D80-B20 Diesel ID ▲ NO ▼NO2 ▲ with increase in At Low EGR At Low EGR
diesel engine nol (B) quantity  50 mg/cycle, D60-B40 ITE ▲ o 1% with increase in butanol fraction. 3 3
CA50 at 8° CA ATDC, EGR for B40 butanol fraction. B40 E Zero At High EGR At High EGR
upto 65% ▼ ▼
▼ CH4 with increase in
butanol fraction.
[75] 6-cylinder, 4S, CR:17.3:1, Diesel (D)þ BMEP 0.3MPa, 1000 rpm D85-IB15 ULSD#2 At low EGR, BSFC 3 ▼ n/a ▲
CRDI diesel engine with a Butanol (B) BMEP 0.5 MPa, 1000 rpm D70-IB30 3 At Low EGR, ▼ At Low EGR, 3 CO IB 4CO B
WC EGR system Diesel (D)þ iso- EGR rates. D85-B15 At retarded At high EGR, 3 At high EGR, ▲ At low EGR,
butanol (IB) Injection timing advanced D70-B30 injection At retarded At retarded injec- 3
and retarded by upto 6°. timing, BSFC ▼ injection tion timing, ▼ At high EGR,
timing, ▼ ▲
At retarded
injection
timing, ▲
[93] 4-cylinder, 4S, turbo- Diesel (D)þ Buta- Variable loads, D80-B20 0# Diesel Peak power High load ▼ ▲ with increase in Low load
charged,CR:18:1,inter- nol (B) 2000 rpmVariable loads, D70-B30 4.6% Low load 22.7% butanol ▼ High load
cooled, high-speed, 4000 rpm D60-B40 BSFC ▲ with 13.4% Max load B40
CRDI diesel engine for increase in Max load B40
passenger-car butanol.
equipped with variable BTE ▲ with
geometry increase in
turbocharger butanol.
BSFC ▲ 5.7%
BTE ▲ 4.3%
Max load B40
[76] 1-cylinder, 4S, CR:16:1, Diesel (D)þ 1400 rpm, Injection timing D80-B20 Diesel ID ▲ ▼ 32.8% n/a n/a
WC CRDI diesel engine Butanol (B)  8° CA ATDC D80-SB20 ITE At low EGR, ▼ At low EGR, 3 At low EGR, 3 At low EGR,
Diesel (D)þ 2- Diesel injection quantity At low EGR, 3 At high EGR, 3 At high EGR, ▲ At high EGR, ▲ 3
butanol (SB)  50 mg/cycle. Injection At high EGR, ▼ At high EGR,
pressure – 1300 bar. ▲
EGR rates 0–62%
[16] 4-cylinder, 4S, RP:66KW, Diesel (D)þ Loads, Variable speeds. D95-B5 D2 n/a 10.3% 55.5% 21.4% 35.7%
CR:19.5:1, TDI diesel Butanol (B) D90-B10 32.3% 77.8% 71.4% 57.1%
engine. D80-B20 54.4% 85.1% 214% 71.4%

93
 94
Table 4 (continued )

Ref Engine Fuel Test conditions/variables Blend Reference fuel Performance NOx Soot HC CO
designation

75% load 75% load 75% load at 1500 rpm 75% load at
at 1500 rpm at 1500 rpm 1500 rpm
[114] 6-cylinder, 4S, WC, Diesel (D)þ BMEP 0.70 MPa, 1330 rpm D70-B30 Diesel BSFC 3 ▼ ▼ ▼ ▼
CR:16.8:1, turbo-charged, Butanol (B) Injection pressure –
CRDI diesel engine 160 MPa, Medium
EGR 440%
[94] Turbo-charged, CRDI Diesel (D)þ ESC (European Stationary D90-B10 Diesel n/a ▲ ▼ in 50-73% mass ▲ Significant for B20 ▲ Sig-
diesel engine Butanol (B) Cycle) test D80-B20 of PM nificant for
B20

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
[95] 4-cylinder, 4S, turbo- Diesel (D)þ BMEP 0.8 MPa, 2500 rpm, D80-B20 LSD BSFC ▼ ▲ 20% Smokeless n/a n/a
charged, CR:17.5:1, WC, Butanol (B) Low injection pressure
CRDI diesel engine (100 MPa) than diesel
injection (120 MPa)
[77] 1-cylinder, 4S, WC, Diesel (D)þ 1500 rpm, Injection timing D80-B20 Diesel ID ▲ IB 4SB4 NB 4TB At low EGR, ▼ Soot ▼
CR:16:1, CRDI Butanol (B) – 8°CA BTDC, Flow rate of D60-B40 BTE ▲ with At high EGR, 3
diesel engine Diesel (D)þ diesel – 60 mg/cycle. D80-SB20 increase in
with EGR system. sec-Butanol (B)EGR rates – 0–62% D60-SB40 butanol.
Diesel (D)þ D80-IB20
iso -Butanol (B) D60-IB40
Diesel (D)þ D80-TB20
tert-Butanol (B) D60-TB40
TB 4NB 4SB 4IB At low EGR, 3 At low EGR, 3
At low EGR, 3 At high EGR, ▲ At high EGR, ▲
At high EGR, ▲
[121] 1-cylinder, 4S, WC, Diesel (D)þ IMEP 1.0 MPa D60-B40 0# Diesel Cylinder ▲ ▼ ▲ ▲
CR:16:1, CRDI Butanol (B) 1400 rpm pressure ▲
diesel engine EGR rates – 0– 65% ID ▲
with EGR system.
[96] 1-cylinder, 4S, AC, DI Diesel (D)þ Variable loads, 3000 rpm. D95-B5 ULSD n/a n/a PM mass con- - n/a
diesel back-up power Butanol (B) D90-B10 centration ▼ with
generator. D85-B15 increase in
D80-B20 butanol.
Total particle-
phase PAHs
concentration
a. B5, B10
▲ B15, B20
[97] 4-cylinder, CR:17.1:1, Diesel (D)þ Variable loads, Variable D95-B5 Diesel n/a n/a B20 – ▲ Particle B10 ▲ formaldehyde -
turbo-charged, CRDI die- Butanol (B) speeds. D90-B10 numbers smaller emissions.
sel engine D80-B20 than 50nm. IHC, ethylene
The total mass of and benzene ▲ with
particles smaller increase in butanol.
than 50 nm. Low load
B5 ▼ 18.5%
B10 ▼ 31.1%
B20 ▲ 20.5%.
[98] 4-cylinder, 4SCR:17.1:1, Diesel (D)þ European Stationary Cycle D95-B5 Diesel n/a NOx ▼ all loads Total mass of PM At low load, At low
turbo-charged, CRDI die- Butanol (B) (ESC) test D90-B10 NO2 ▲ with B5 ▼ 70–90% Formaldehyde emis- load, ▲
sel engine with cooled – 13 mode D80-B20 increase in B10 ▼ 60-80% sions for all blends. ▲
EGR system butanol. B20 ▼ 30-60% THC ▲
Formaldehyde emis-
sions for all blends ▼
For B20,
PAHs ▲
High load
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115 95

▲ – increases; ▼ – decreases; 3 – no change; 4S – Four stroke; DI – Direct injection; CRDI– Common-rail direct injection; RP – Rated power; CR – Compression ratio; AC – Air-cooled; WC – Water-cooled; HD – Heavy duty; HS –

release rate; BMEP – Brake mean effective pressure; BP – Brake power; ITE – Indicated thermal efficiency; BTE – Brake thermal efficiency; BSFC – Brake specific fuel consumption; PP – Peak pressure; ID – Ignition delay; EGR –
High speed; DOC – Diesel oxidation catalyst; DPF – Diesel particulate filter; CA – Crank angle; ATDC – Above top dead center; BTDC – before top dead center; LSD – Low sulfur diesel; ULSD – Ultralow sulfur diesel; HRR – Heat
and 450 Nm). The results confirmed that peak cylinder pressure
and heat release rate increases with increase in iso-butanol con-
tent in the blends. There was an increase in BSFC with an asso-
ciated decrease in BTE for increasing blend proportions.
For B2, ▲ 24.43% For B4, n/a

So far majority of the studies have focused only on steady state

at full load (115 Nm) and
▲ 31.30%For B6, ▲ 29.01%

performance of diesel engines while a major portion of the daily

driving cycles involved transient conditions. Legislations in US,
Europe and Japan have been drawing the attention of manu-
facturers and researchers to the transient operation of diesel
4000 rpm.

engines by requiring certifications for transient cycles for new

vehicles. There was a definitive absence of literature that studied
the behavior of diesel engines fueled with butanol/diesel blends in
transient operating conditions at that time. In this context, Rako-
poulos et al. [89] investigated the formation mechanisms of nitric
a. 21.75% for B4

oxide (NO), smoke, and combustion noise radiation during hot

@ 2500rpm

starting for various alternative fuel blends in a turbocharged diesel

engine. The test matrix included neat diesel and 30% (v/v) blends
of bio-diesel or n-butanol. They conducted a variety of starting
▼

tests and found that n-butanol/diesel blend decreased the smoke

opacity significantly but increased NOx emission notably in com-
For B2, ▼ 1.47%

5.03%

parison with neat diesel and biodiesel/diesel blend. They further

@2000 rpm

@3000 rpm

@4000 rpm

concluded that butanol/diesel blends had less impact in the

transient performance and overall combustion noise radiation of
B4, B6

2.74%

the engine.
▼

In another investigation by the same research group [90], tests

were conducted in the same engine to study the mechanism of
and

▼@ 2000 and
Peak pressure 3

combustion noise radiation during various accelerations for 30%

(by volume) biodiesel blend and 25% (v/v) butanol blend with
2000
3000 rpm

3000 rpm
Efficiency
HRR 3

diesel. They found that n-butanol/diesel blend emitted highest

BSFC

noise emissions in all transient tests conducted when compared to

@

biodiesel blend and neat diesel operation. Meanwhile, Armos et al.

[91] evaluated the effects ethanol and butanol/diesel blends on
pollutant emissions during moderately cold and warm start pro-
cesses in a turbocharged DI diesel engine equipped with a
Diesel

common-rail injection system, cooled exhaust gas recirculation

(EGR), diesel oxidation catalyst (DOC) and a diesel particulate filter
(DPF). Their results indicated that both alcohol/diesel blends pro-
duced combustion instabilities at cold starting conditions. How-
D98-B2
D96-B4
D94-B6

ever, the blends had a favorable effect on smoke opacity and

particulate concentration with no changes in NOx emissions. It
was also reported that butanol/diesel blend produced slightly
higher gaseous emissions than ethanol/diesel blend.
2000 rpm, 3000 rpm and

Carbonyl compounds are non-regulated emissions that have

high atmospheric reactivity and carcinogenic potential. Ballesteros
Variable loads at

et al. [92] examined the carbonyl emissions of a 4-cylinder DI

diesel engine fueled with bioethanol and butanol/diesel blends
4000 rpm.

under four modes of the European driving cycle. Their results

indicated that butanol blend presented lesser carbonyl emissions
than bioethanol blend.
Siwale et al. [16] compared the effects of 5%, 10%, and 20% (v/v)
of n-butanol/diesel blends and 30% biodiesel blend with similar
Diesel (D)þ
Butanol (B)

diesel fuel admixed to 5% or 7.5% of bioethanol in a turbo-charged

Exhaust gas recirculation; n/a – not available.

diesel engine. They found that NOx, CO, unburned hydrocarbons

(UHC) and soot emissions reduced substantially with n-butanol/
diesel blends. Their results indicated a more stable combustion
4S,
RP:48KW, CR:18.25:1,
turbo-charged,

process for butanol blends than diesel fuel and a distinct premixed
CRDI diesel engine

combustion phase due to the increased ignition delay with

RENAULT K9K 700

increase in butanol content in the blends. Similarly, Chen et al. [93]

also reported a slightly increased combustion pressure and accel-
4-cylinder,

erated burning rate with little impact on maximum power and

torque using butanol/diesel blends when compared to diesel. They
WC,

used 20%, 30% and 40% (v/v) of butanol in a high speed DI diesel
engine meant for passenger-car applications and recorded high
[99]

NOx, HC emissions with decreased CO and smoke emissions at

high load conditions.
96 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
Choi et al. [94] investigated the effect of bio-butanol addition
(10 and 20% v/v) to diesel on the emissions of a turbo-charged
common rail DI diesel engine under the European Stationary Cycle
(ESC) test. They observed that both formaldehyde and formic acid
emissions to increase in low loading of ESC 7, 9, 11 and 13 mode.
With the usual increase in NOx emissions, they found that mass of
particulate matter (PM) to be reduced by upto 73% using bio-
butanol blends.
Optical investigations carried out by Merola et al. [95] con-
firmed that butanol/diesel blends stimulated faster formation and
higher concentration of OH radicals in an optically accessible
combustion chamber of a single cylinder engine which advances
the soot oxidation phase and promotes smokeless combustion in
early injection conditions. The oxygen atoms in the alcohol con-
sume soot precursors through the formation of OH radicals, and
result in a decrease of soot emission.
Particulate matter emitted by diesel engines is characterized by
different sizes with different health effects being associated with
particles of different diameters. Recently, an investigation
regarding the influence of butanol–diesel blends (5–20% v/v in
diesel) on particulate emissions of a non-road diesel engine was
carried out by Zhang et al. [96]. Their results indicated that blends
containing higher than 10% butanol showed increased poly-cyclic
aromatic hydrocarbon (PAH) emissions. It was found that increase
in butanol content in the blends results in decreased elemental
carbon (EC) emissions and increased organic carbon (OC) emis-
sions when compared to ULSD. It was also discovered that mass
concentration of PM2.5 (with aerodynamic diameter less than
2.5 μm) reduced considerably with high butanol blends at high
engine loads in this study. This is noteworthy because PM2.5
represents a group of inhalable particles that can penetrate the
human respiratory system further than larger particles.
Individual hydrocarbon (IHC) emissions from the diesel engines
are associated with the formation of PM. Important studies related
to the analysis of IHC and PM from diesel engines fueled with
butanol/blends were studied by Choi et al. [97] in a turbo-charged
CRDI diesel engine. They found that more ethylene and benzene
were emitted under low load conditions and their amounts
increased with increased butanol content in the blends. 20%
butanol blend reportedly increased particle numbers smaller than
50 nm and formaldehyde (HCHO) emissions increased for blends
with butanol content above 10% when compared to neat diesel
operation.
In another study, Choi et al. [98] studied the performance and
emissions of the same engine fueled with 10% and 20% blend v/v of
butanol with diesel under the ESC test. This study revealed that
blends with butanol content higher than 20% v/v in diesel con-
tributes toluene and benzene that can trigger the formation of
PAH. This particular blend also caused a significant increase in THC
and CO emissions and a modest increase in HCHO and HCOOH
emissions under ESC 7, 9 and 11 modes compared to baseline
diesel operation. It was suggested that 5% butanol/diesel blend
could be chosen for low PM mass concentration and low emissions
of PM under 50 nm.
A majority of previous studies have investigated the effects of
butanol blend ratios ranging from 10 to 40% on the performance
and emissions of diesel engines. Lately Sahin et al. [99] selected
lower butanol ratios of 2%, 4% and 6% with the perspective to
reduce cost, BSFC and tendency of diesel knock. Experiments were
performed in a 4-cylinder, turbo-charged CRDI diesel engine under
different loads and engine speeds. 2% blend is determined to be
favorite owing to its slightly higher cylinder pressure and heat
release rate (HRR) with slight reduction in BSFC and improved
efficiency at 2000 rpm when compared to diesel. HC emissions
increased for all blends while NOx emissions decreased at certain
speeds for 2% blend. While smoke emissions dropped for all
blends, 4% blend showed maximum reduction in smoke.
3.2.2. Summary
The above referenced studies collectively demonstrate that
butanol-addition to diesel leads to the following effects on per-
formance and emission of a diesel engine in comparison with neat
diesel operation.
 Ignition delay increases with increasing butanol content in the
blends as a result of lower cetane number of butanol. There is a
slight increase in peak combustion pressure and peak heat release
rate slightly with butanol addition as a result of enhanced pre-
mixed combustion phase caused by a prolonged ignition delay.
 BTE generally increases with increasing butanol content in the
blends. There are many reasons attributed to the increase
in BTE.
 Longer ignition delays as a result of lower cetane number of
butanol causes a wider fraction of the fuel to burn during the
enhanced premixed combustion phase.
 The enhanced oxygen content of butanol improves the combustion
process, particularly during the diffusion combustion phase.
 Higher burning velocities lead to higher efficiency. Butanol has
higher burning velocity than diesel. The laminar burning velocity
of diesel is 33 cm/s [100] and that of butanol is 45 cm/s [101].
 In case of iso-butanol diesel blends, an increase in BTE was
reported only with lower blends (5 and 10%) at high speeds [8].
However, BTE decreased for all other blends corresponding to the
increasing BSFC and decreasing calorific value of the blends [8,84].
 BSFC decreases invariably with increasing butanol content in
the blends. The heating value of butanol is approximately 21%
lower than diesel and hence the engine requires more amount
of fuel to produce the same output torque.
 NOx emissions generally decrease with increasing butanol
content in the blends. This is due to the engine running overall
leaner and the temperature lowering effect of butanol (due to
its lower calorific value and higher heat of evaporation) dom-
inating the possibly higher temperatures during the premixed
combustion phase as a result of longer ignition delay (due to its
lower cetane number). This is a delicate balancing which can
weigh more on the either side depending on the specific engine
and its operating conditions [52].
 Smoke emissions consistently decreased with increasing buta-
nol content in the blends. The higher oxygen content and lower
carbon content of butanol can be attributed to reduced smoke
emissions [19]. The presence of fuel-bound oxygen in the blends
especially in locally rich zones improved the combustion
process resulting in less smoke emissions [10].
 HC emissions increased with increasing butanol content in the
blends. The slower evaporation and poorer air–fuel mixing due
to the higher latent heat of evaporation of butanol blends and
fuel impingement on the walls due to increased spray pene-
tration are the major causes for unburned hydrocarbons.
 Butanol/diesel blends presented higher carbonyl compounds
emissions than diesel. However its lower than ethanol/diesel
blends [92].
 Butanol/diesel blends containing butanol higher than 10%
showed increased PAH emissions. Also it was also reported that
increase in butanol content in the blends results in decreased EC
emissions and increased OC emissions [96].
Butanol can replace diesel by upto 40% in volume and can be
used in diesel engines with better fuel conversion efficiency and
low emissions.
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
3.2.3. Future research directions
 Further studies are required to study the effects of using buta-
nol/diesel blends higher than 40% in volume in diesel engine
performance and emissions.
 Studies to investigate the effects of butanol/diesel blends on
engine performance and emissions at high altitude conditions
and also at low ambient temperatures (between  20 °C and
5 °C) are required.
 The bio-degradability and long-term stability of butanol/diesel
blends under sunlight and heat exposure should be carried out.
3.3. Use in low temperature combustion (LTC) applications
Simultaneous reduction of smoke and NOx emissions is very
difficult to achieve in diesel engines due to the inherent trade-off
relation between them. Low temperature combustion (LTC) is a
strategy that offers promising solution to reduce both NOx and
smoke emissions simultaneously with improved combustion effi-
ciency [102]. The key characteristic of LTC is a thoroughly pre-
mixed fuel/air mixture that burns at low temperature following a
long ignition delay period [103]. Exhaust gas recirculation (EGR)
and retardation of injection timing are considered to be the most
effective approaches to achieve LTC mode [104]. Modulated
kinetics (MK) is a type of LTC discovered by Nissan [105,106] that
uses medium EGR levels and retarded injection timing to prolong
the ignition delay [103]. Introducing high EGR can suppress smoke
and NOx formation by extending the ignition delay (for effective
pre-mixing) and lowering the overall combustion temperature
respectively [102]. However, high EGR rates can deteriorate com-
bustion and eventually decrease the performance of the engine
due to high levels of HC and CO emissions. Retarding the injection
timing also extends the ignition delay and provides ample time for
fuel/air mixing but results in reduction of brake thermal efficiency
and increased smoke density [107].
Therefore to mitigate the effects of high EGR rates and retarded
injection timing, a fuel with lower cetane number and higher
volatility like an alcohol can be utilized. In this way, a partially
premixed LTC mode with low rates of soot and NOx formation may
be realized without the use of high EGR rates [108–110]. Higher
alcohols like butanol can be suitable candidates for LTC because
they can offer (a) resistance to auto-ignition (b) longer ignition
delay period (due to low cetane number) for sufficient mixing
(c) faster vaporization (due to high volatility) for increasing the
mixing rate. Liu et al. [64] has shown in an constant volume
combustion chamber study that soot concentrations increased
dramatically for soybean biodiesel from 800 to 1000 K at 10.5%
oxygen, while such increases are not found for butanol/biodiesel
blend and neat butanol fuel and indicated that indicating that
proper choosing of the fuel will be very important to achieve high
efficiency and clean low-temperature combustion. In a study that
measured the ignition delay of n-heptane/n-butanol mixtures and
neat n-butanol behind reflected shock waves, it was found that
only a very limited part of n-butanol participates in the low-
temperature branching due to the influence of OH group, leading
to an increased ignition delay times at low temperature [111].
3.3.1. Combustion, performance and emission characteristics
In this section, research studies that evaluated the capability of
butanol in enabling LTC mode in diesel engines are discussed. A
summary of these investigations are presented in Table 5.
One of the early studies that utilized n-butanol to achieve LTC
in diesel engines was conducted by Tornatore et al. [112]. Com-
bustion tests were carried out in an optically accessible diesel
engine using 20% butanol/diesel blend under different injection
97
timings and EGR rates. A partially pre-mixed LTC was attained at
late injection timing coupled with high EGR rate of 50%. Sub-
stantial reductions in smoke and NOx emissions were obtained
with a slight drop in efficiency. It was found that a good com-
promise between efficiency and emissions can be improved by
using an early injection timing in which a mixing controlled
combustion (MCC) LTC can be realized. Valentino et al. [110]
reported the effects of start of injection (SOI), O2 concentration at
intake and injection pressure on the combustion and emission
characteristics of a turbo-charged, water-cooled, direct-injection
diesel engine, equipped with a common-rail injection system
using 40% gasoline and 40% n-butanol blended-diesel fuel. It was
established that better management of injection pressure, O2
concentration at intake and injection timing would enable partial
premixed combustion by extending the ignition delay for both
blends. Particularly, n-butanol/diesel blend showed better effi-
ciency than gasoline/diesel blend with reduced emissions at
moderate injection pressures of 100–120 MPa.
In an another study using the same engine infrastructure,
Valentino et al. [109] studied the effects of 20% and 40% n-butanol/
diesel blends by varying the injection pressure, injection timing
and intake O2 concentration. The results showed that both blends
enabled partially premixed LTC and allowed early SOI and required
moderate injection pressure (100–120 MPa) with 19% oxygen
concentration at the intake to achieve improved NOx and drastic
reductions in smoke emissions with slightly worsened specific fuel
consumption (by 5–7%). Further, high combustion noise emissions
were reported from 40% n-butanol/diesel blends when compared
to diesel operation.
Zhang et al. [102] assessed the performance and exhaust
emissions of a modified single cylinder heavy duty diesel engine
using 20% and 40% n-butanol/diesel blends with a fixed CA50
timing and EGR rates upto 65%. The injection quantity of all test
fuels was fixed to keep the same cycle heat value. The engine ran
at maximum torque speed of 1400 rpm. The addition of n-butanol
caused decrease in the emissions of smoke, CO and THC at high
EGR rates. A slight increase of ITE (1%) was obtained with the
highest blend. While the proportion of methane (CH4) increased
with increase in EGR rates, n-butanol addition was found to lower
it. Soloiu et al [113] demonstrated that LTC and Premixed charge
compression ignition (PCCI) can be enabled using the combination
of butanol PFI and bio-diesel DI to achieve simultaneous reduction
of NOx (74%) and smoke (98%) emissions at 3 bar IMEP (indicated
mean effective pressure) in a single cylinder DI diesel engine with
a omega combustion chamber in the piston.
Chen et al. [114] conducted an experimental study to evaluate
and compare the combustion and emission characteristics of a
multi-cylinder diesel engine fueled with 30% blends each of
dimethyl-furan (DMF)-diesel (D30), n-butanol-diesel (B30) and
gasoline-diesel (G30) with combustion phasing and EGR. The
engine was operated at a constant speed of 1330 rpm and a con-
stant load of 0.70 MPa. The injection pressure was kept constant at
160 MPa. It was concluded that DMF is superior in controlling the
soot emissions when compared to gasoline and n-butanol due to
its longer ignition delay and fuel-bound oxygen. Both D30 and B30
were found to improve NOx/PM trade-off remarkably without
compromising fuel efficiency at medium EGR rates ( o40%). Both
DMF and n-butanol blends were found to have small effects on
NOx, THC, CO emissions and BSFC.
While investigating the suitability of different fuels (gasoline,
ethanol, n-butanol and diesel) and various fuel intake strategies
for LTC at high-load operation, Han et al. [115] found that n-
butanol when injected at the intake port, deteriorated emission
performance due to its early auto-ignition. It was demonstrated
that n-butanol is more suitable than diesel fuel for enabling LTC
 98
Table 5
Summary of investigations that used butanol for enabling LTC in diesel engines.

Ref. Engine Fuel Alcohol Injection EGR Reference fuel Test conditions Trade-off relation Performance HC / CO emissions
Composition

[112] 1-cylinder, 2S, CR:10.1:1, Diesel þ 20% (by vol.) Direct Injection Two EGR rates LSD 500 rpm, Diesel injection Simultaneous reduction of 3 No information.
CRDI diesel engine with n-butanol 0% and 50%. quantity – 30 mg/cycle at NOx and smoke.
external high swirl opti- the pressure of 70 MPa.
cally accessed combus- Injection timings.
tion bowl.
[110] 4-cylinder, turbo- Diesel þ 40% (by vol.) Direct injection. EGR in terms of LSD BMEP 0.5 MPa Simultaneous reduction of ▲ ▲
charged, CR:17.5:1, WC, n-butanol oxygen reduc- 2000 rpm NOx and smoke.
CRDI diesel engine tion from 17% BMEP 0.8 MPa

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
to 21% 2500 rpm
Injection timings, Injec-
tion pressures.
[109] 4-cylinder, turbo- Diesel þ 20% and 40% (by Direct injection. EGR in terms of LSD BMEP 0.8 MPa Simultaneous reduction of BSFC HC increases,
charged, CR:17.5:1, WC, n-butanol vol.) oxygen reduc- 2500 rpm NOx and smoke. ▼ 5-7% No information
CRDI diesel engine tion from 19% Start of injection, on CO emissions.
and 19.5% Injection pressure.
[102] Modified 1-cylinder, 4S, Diesel þ 20% and 40% (by Direct injection. 0–65% EGR Diesel Engine speed – 1400 rpm NOx and smoke decrease ▲ No change up to a
CR:16:1, WC, CRDI diesel n-butanol vol.) Injection quantity upto certain EGR range certain EGR rate
engine, Diesel – 50 mg/cycle. with increase in and increases
B20 – 50.8 mg/cycle performance. beyond that.
B40 – 51.7 mg/cycle.
CA50 fixed at 8° CA ATDC.
[113] 1- cylinder, 4S, Peanut methyl Two Fixed Port-fuel injec- No EGR ULSD#2 IMEP 1–3 bar at 800 rpm. Simultaneous reduction of ▲ No information.
RP:16.9KW, CR:16:1, DI ester Biodiesel flow rates: tion of n-butanol (Low load and Idling NOx and smoke.
diesel engine (PME) þn- 0.4 Kg/h Direct injection speeds)
butanol 0.6 Kg/h of biodiesel
[121] 1-cylinder, 4S, RP:167KW, Diesel þ 40% (by vol.) Direct injection. 40% EGR 0# Diesel IMEP 1.0 MPa NOx increases and Smoke 3 3 up to a certain
CR:16:1, WC CRDI diesel n-butanol 1400 rpm unaffected up to a certain EGR rate and ▲
engine with EGR system. EGR rate with no change beyond that.
in performance.
[115] 4-Cylinder (Re- Neat – Port injection 51–57% EGR Diesel Port injected n-butanol. Ultra-low NOx and soot No information. No information.
configured to n-butanol HCCI combustion Diesel pilot is disabled. emissions.
1-cylinder), 4S, CRDI mode
diesel engine Direct Multi- 4 60% EGR Diesel Injection pressure, intake Simultaneous reduction
pulse injection boost and injection of NOx and smoke.
strategy. timing
[75] FORD LION V6 6-cylinder, Diesel þ 0–30% (by vol.) Direct injection. 0–35% EGR. ULSD2 BMEP 0.3MPa Simultaneous reduction of HRR ▲ No information on
4S, CR:17.3:1, CRDI diesel n-butanol 1000 rpm NOx and smoke at low PP ▲ HC emissions.
engine with a WC EGR Diesel þ BMEP 0.5 MPa loads. At low EGR, CO emissions, At low
system iso-butanol 1000 rpm BSFC 3 EGR, 3
Injection At Retarded At high EGR, ▲
timing advanced injection At Retarded injec-
and retarded by upto 6°. timing, tion timing, ▲
CA. BSFC ▼
[77] 1-cylinder, 4S, WC, Diesel þ 20% and 40% (by Direct injection. 0–65% EGR Diesel 1500 rpm. NOx decreases and smoke 3 No change up to a
CR:16:1, CRDI diesel n-butanol vol.) Injection timing – hardly increases up to a certain EGR rate
engine with EGR system. Diesel þ 8°CA BTDC certain EGR rate with no and increases
sec-butanol Diesel flow rate – change in performance. beyond that.
Diesel þ 60 mg/cycle.
iso –butanol
Diesel þ
tert-butanol
[130] ISUZU 4JA1 Diesel þ 10% n-butanol by n-butanol fumi- No. ULSD Two Mode Simultaneous reduction of BSFC ▲ 19.9% ▲
4-cylinder, 4S, n-butanol energy basis with gation and igni- M2 (BMEP 0.478 MPa NOx and smoke with at low load
RP:59KW, CR:18.4:1, diesel. tion by direct 2410 rpm) decrease in performance. BTE ▼
 turbocharged, DI auto- injection of M4 (BMEP 0.216 MPa 13.2% at
motive diesel engine diesel. 2410 rpm) low load
BTE 3
at high load
[128] 6-cylinder, 4S, WC, Diesel þ 47% Port fuel Port injection of 45% EGR. Diesel IMEP 1.0 MPa Simultaneous reduction of ▼ ▲
CR:16:1, heavy duty CRDI n-butanol injection of n-butanol and 1900 rpm (Close to NOx and smoke
diesel engine with a port n-butanol ignition by direct European Stationary
fuel injection circuit. injection of diesel. Cycle (ESC) tests
B speed)
[76] 1-cylinder, 4S, CR:16:1, Diesel þ 20% (by vol.) Direct injection. 0-62% EGR Diesel 1400 rpm, Injection NOx decreases and smoke 3 At low EGR, 3
WC CRDI diesel engine. n-butanol timing – 8° CA ATDC. hardly increases up to a At high EGR, ▲
Diesel þ Diesel injection quan- low EGR rate with no
2-butanol tity – 50 mg/cycle. change in performance.
Injection pressure –

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
1300 bar.
[117] 1-cylinder, 4S, CR:16:1, Gasoline þ 10%, 20%, 30% (by Direct injection. 0–45% EGR 93# Gasoline 1500 rpm, IMEP Soot emissions decreases ▲ ▼ slightly
CRDI diesel engine n-butanol vol.) 0.9 MPa by 85% but NOx is largely
CA50 87 0.5°CA ATDC not affected with reference
Injection pressure to gasoline operation.
40 MPa
[124] 1-cylinder, 4S, CRDI die- n-butanol 100% Single-shot injec- EGR Diesel Medium engine loads Low NOx and smokeless ▲ ▲
sel engine tion strategy (6–8 bar IMEP) emissions with improved
efficiency

▲ – increases; ▼ – decreases; 3 – no change; 4S – Four stroke; DI – Direct injection; CRDI– Common-rail direct injection; RP – Rated power; CR – Compression ratio; AC – Air-cooled; WC – Water-cooled; CA – Crank angle; ATDC –
Above top dead center; BTDC – before top dead center; LSD – Low sulfur diesel; ULSD – Ultralow sulfur diesel; HRR – Heat release rate; IMEP – Indicated mean effective pressure; BMEP – Brake mean effective pressure; BTE – Brake
thermal efficiency; BSFC – Brake specific fuel consumption; CA50 – 50% burn-point; PP – Peak pressure; ID – Ignition delay; EGR – Exhaust gas recirculation;

99
100 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
under high-pressure direction injection. The study concluded that
less-reactive ethanol is suitable for high load LTC enabling.
Gu et al. [75] presented a study that first demonstrated the use
of iso-butanol in enabling LTC in diesel engines. Experimentation
was carried out at light/medium loads in a common-rail direct-
injection diesel engine with a water-cooled EGR system using two
blend proportions (15% and 30% v/v) of iso-butanol/ diesel and n-
butanol/diesel blends. Various combinations of EGR and SOI were
used. It was concluded that a combination of low EGR rate (20-
23%) and retarded injection timing and blending iso-butanol can
deliver acceptable fuel economy while maintaining low soot and
NOx emissions at low loads.
Another isomer, sec-butanol was used in a study that compared
and analyzed the effects of fuel properties and oxygenated struc-
tures [76] with other fuels that included n-heptane, iso-octane, n-
butanol and methyl-octynoate. All were blended with diesel by
20% in volume basis and tested under wide range of EGR rates
from 0% to 62% so as to enable both CDC and LTC modes in a single
cylinder common-rail DI diesel engine. The combustion of diesel
blends of both isomers was found to have similar characteristics.
The main conclusion of this study is that, the position of the
hydroxyl radical between n-butanol and sec-butanol had a very
small effect in combustion and soot emissions at 20% blending
ratio. The oxygen in n-butanol is solely responsible for soot
reduction followed by its low cetane number when compared to
diesel. The influence of the boiling point of the blend on soot
emissions is minor.
In a recent work by the same research group [77], the effects of
adding four butanol isomers in diesel fuel (20% and 40% v/v) on
combustions and emissions were evaluated over a wide range of EGR
rates that covered both CDC and LTC mode in a single cylinder CRDI
diesel engine. The comparative results of four butanol-isomer/diesel
blends on some parameters were presented as follows: Ignition
delays: iso-butanol4sec-butanol4n-butanol4ter-butanol. Com-
bustion duration: ter-butanol4n-butanol4sec-butanol4iso-buta-
nol. Soot emissions: ter-butanol4n-butanol4sec-butanol4iso-
butanol. The variations in thermal efficiencies among all the blends
were small. CO emissions are always 10 times higher than THC
emissions in high EGR region.
Iannuzzi et al. [116] compared the consequences of using
gasoline/diesel and n-butanol/diesel fuel blends in a Euro 5 light
duty diesel engine at a mixing ratio of 20:80 v/v at a constant
speed of 2500 rpm and 0.8 MPa BMEP (brake mean effective
pressure) using various injection strategies and intake oxygen
concentration. UHC emissions of butanol blend were found to be
marginally lower than that of gasoline blend and diesel for any
injection strategy. Butanol blend gave worst fuel consumption
among the test fuels due to its low heating value.
Yang et al. [117] attempted to mix n-butanol with gasoline
under LTC conditions. The combined effects of EGR and n-butanol/
gasoline blends (0%, 10%, 20% and 30% by mass) on regulated and
un-regulated emissions of a single cylinder CI engine at an IMEP of
0.9 MPa and engine speed 1500 rpm was explored in this study.
Addition of 30% butanol reduced soot emissions of pure gasoline
by 85% while NOx emissions remained unchanged due to the
higher heat of evaporation and octane number of butanol can-
celling each other's effects. Higher butanol fraction causes higher
proportions of primary IHC like ethylene, propylene, n-Pentane
and iso-Pentane. However aromatic hydrocarbons (AHC) showed
an opposite trend with increasing butanol content in gasoline.
Aldehydes like formaldehyde and acetaldehyde also increased
with butanol addition.
Majority of the reviewed studies primarily focused on the soot
emissions with n-butanol/diesel blend during LTC while a very few
addressed the mechanism of soot precursor formation. This
understanding is significant because the polycyclic aromatic
hydrocarbons (PAH) which are the key components of soot emis-
sions are carcinogenic in nature. The chemical reactions that these
PAHs undergo heavily influence the formation of soot particles. In
this context, Zhou et al. [118] studied the soot precursor emission
characteristics of n-butanol/diesel blend during LTC under the
influence of factors like blending ratio, EGR rate, injection timing,
and intake pressure. Their results indicated that increase in
butanol-ratio caused a delay in formation as well as decrease in
final amount of four types of soot precursors viz. benzene, naph-
thalene, phenanthrene and pyrene. Similar reduction in soot pre-
cursors like benzene was reported with the addition of methanol
[119,120]. With increasing EGR rate, the final amount of benzene
produced increased while the amount of naphthalene, phenan-
threne and pyrene decreased. The final amounts of all soot pre-
cursors increased with increase in intake pressure while early
injection timing caused an early formation of all of them.
An experimental and simulation investigation was carried out
by Chen et al. [121] using a high blending ratio of 40% n-butanol in
a heavy-duty diesel engine under EGR at a constant engine speed
and load and compared with baseline diesel operation. It was
found that n-butanol has higher cylinder pressure, longer ignition
delay and a faster burning rate. In emissions viewpoint, n-butanol
presented higher NOx and CO emissions with lower soot emis-
sions. NOx emissions reduced drastically while soot remained
unaffected under EGR influence. No significant changes in HC, CO
and ITE were found until a EGR ‘threshold’ level is reached after
which they deteriorated intensely.
Zheng et al. [122] studied the effects of two-stage injection
strategies (pilot-main and main-post) on combustion and emis-
sions of a single-cylinder diesel engine under high EGR (46%)
condition using blends of diesel/gasoline, diesel/n-butanol, diesel/
gasoline/n-butanol and pure diesel. It was concluded that adopting
pilot injection close to main injection can effectively reduce the
peak of premixed HRR and maximum ROPR (rate of pressure rise).
Smoke emissions effectively decreased with increasing pilot-main
interval. The post injection strategy also led to lesser NOx emis-
sions when compared to main injection. Smoke emissions of
blended fuels are found to be more sensitive to the variation of
post injection strategy than diesel.
Liu et al. [123] in an attempt to explore the more effective
method to fulfill the challenges of early-injection, investigated
different engine operating parameters like intake pressure,
exhaust gas recirculation (EGR), equivalence ratio, intake tem-
perature, coolant temperature, injection pressure injecting blends
of diesel/gasoline, diesel/n-butanol and dual-fuel over a wide
range of timings from 5° CA ATDC to  70° CA ATDC. It was con-
cluded that soot emissions decreased dramatically as the injection
timing was advanced due to lowered combustion temperature.
Also dual-fuel injection composed by port-injection of gasoline
and direct-injection of diesel was more effective in reducing soot
emissions than that of single direct-injection under the same
gasoline/diesel ratio. Under the same equivalence ratio, the com-
bination of EGR and higher intake pressure presented lower soot
emissions than when EGR is used alone. It was seen that blends of
diesel/gasoline and diesel/n-butanol reduced soot emissions
drastically and pure gasoline or n-heptane presented smokeless
combustion owing to their high volatility.
Recently, Han et al. [124] used a single-shot injection strategy
to fuel a modern common-rail diesel engine with neat butanol at
medium engine loads of 6–8 IMEP. The results were compared
with diesel direct injection. The efficiency was diesel-like with
ultra-low NOx emissions even without EGR usage. Smokeless
emissions were reported at these operating conditions. With the
introduction of EGR, LTC was realized with simultaneous reduction
of NOx and smoke emissions with improved efficiency. n-butanol
combustion is usually associated with a rapid HRR within a short
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
combustion duration resulting in high rates of pressure rise. The
use of EGR delayed ignition and slowed down combustion rates
but deteriorated combustion resulting in increased HC and CO
emissions. Misfire incidences were also observed with high rates
of EGR under single-shot injection strategy. To overcome these
setbacks, the same research group [125] devised a strategy that
can improve combustion control with neat-butanol operation. It
was found that multi-phase injections with moderate EGR can be
the solution. This strategy also helped minimizing the exhaust
emissions with improved efficiency. These studies provided a
testimonial that diesel can be fully replaced by cleaner renewable
butanol for improved emissions and performance.
Very recently, Rajesh et al. [126] showed that the combination
of EGR rates of upto 30%, iso-butanol addition of upto 40% v/v and
retarded injection timing by 2° CA BTDC simultaneously reduced
NOx emissions from 1284 to 749 ppm and smoke opacity from
20.7% to 1.9%. Also, it was reported that higher iso-butanol/diesel
blends present better EGR tolerance while maintaining simulta-
neous reduction of NOx and smoke emissions.
3.3.2. Summary
A collective conclusion is that with proper control strategies
over engine operating parameters such as air and fuel handling,
the potential of butanol and its isomers can be tapped for enabling
LTC on diesel engines. When compared to neat diesel operation,
the effects on emissions and performance of the engine under LTC
operation using butanol can be summarized as follows:
 Butanol offers great resistance to auto-ignition which provides
adequate time for thorough mixing of air and fuel. Higher
volatility of butanol improves the mixing rate that helps to
enhance the homogeneity of the cylinder-charge. Further the
fuel-bound oxygen of butanol improves oxygen availability in
fuel-rich zones, consumes soot-precursors and contributes to
soot reduction.
 The higher heat of evaporation of butanol lowers the combus-
tion temperature which affects the formation of NOx. The use of
high EGR rates also reduces NOx emissions by lowering the
combustion temperature besides extending the ignition delay
that helps thorough pre-mixing of cylinder-charge.
 While simultaneous reduction of NOx and smoke emissions is a
common feature of LTC, high EGR rates generally increases HC
and CO emissions.
 The management of injection pressure, intake O2 concentration
and injection timing can have better control over LTC which
enables a premixed combustion by extending the ignition delay
[109].
 Engine performance is usually enhanced due to better mixing of
fuel and air. However, best emission results generally involved a
penalty in BSFC and BTE of an engine.
3.3.3. Future research directions
 The use of high EGR rates in LTC can cause excessive engine
wear, carbon-deposits on piston head and degradation of
lubrication oil (increase in oil-soot loading and acid value).
Hence, further studies are required to assess long-term engine
durability under LTC operation using butanol in collaboration
with engine manufacturers.
 Advanced material and surface technologies can be developed
for improving friction and wear performance under high EGR
environments as in butanol LTC operation.
 The best combination of injection pressure, intake O2 con-
centration and injection timing for better LTC control in an
engine can be investigated using multi-response optimization
techniques.
101
3.4. Butanol Dual-fuel injection
Dual-fuel injection is one of the methods by which diesel
technology can be made available to low cetane number alcohols
like butanol. It involves injecting a pre-determined quantity of
butanol into the intake manifold of the engine using an injector
which is connected to a separate fuel tank with dedicated fuel
lines and controls [127]. While blending is generally considered to
be the most practical method for butanol as it is known to form
stable mixtures with diesel, dual-fuel injection offers the following
advantages,
 Higher percentage of butanol can be utilized, i.e. higher energy
share from renewable fuels can be obtained [128]. At this
juncture, it should be noted that butanol/diesel blends above
35% do not satisfy the lubricity requirements according to
European EN 590 norms [12].
 Water-containing (hydrous) butanol can be used.
 The engine can always switch between dual-fuel and neat diesel
operation as and when required.
 Butanol supply can be dynamically controlled. This strategy
allows flexibility to adjust the fraction of butanol to be injected
that has to take part in combustion based on engine load con-
ditions [129].
 Evaporation of butanol in intake air can cause a cooling effect
and lower the temperature and increase the density of the
mixture. This implies that more amount of evaporated butanol–
air mixture can enter the combustion chamber which can
improve the power output of the engine [127].
 Mixing quality can improve due to the availability of ample time
while butanol and air diffuses through the intake manifold upto
the combustion chamber.
 Evaporation losses can be minimized when compared to blends
[130].
3.4.1. Combustion, performance and emission characteristics
In this section, the available literature that studied the effects of
different percentages of butanol PFI on combustion, performance
and emission characteristics of various diesel engines at different
test conditions were reviewed. A summary is presented in Table 6.
Michikawauchi et al. [131] investigated the possibility of
reducing NOx emissions and improving efficiency using both
butanol fumigation (50% volume ratio) and butanol/diesel blends
(50% v/v) in a diesel engine. The results showed that butanol
fumigation is more effective than the blends. While fumigation
reduced NOx emissions by 73%, the blends managed only 61%
reduction at medium loads. It was further found that the trade-off
between NOx and smoke emissions improved without affecting
engine efficiency at medium and high loads. Soloiu et al. [113]
demonstrated that LTC and PCCI can be enabled using the com-
bination of butanol PFI and bio-diesel DI to achieve a massive
reduction of NOx (74%) and smoke (98%) emissions simultaneously
at low/medium loads in a single cylinder DI diesel engine with a
omega combustion chamber in the piston.
While assessing the suitability of four different fuels (gasoline,
diesel, n-butanol and ethanol) for high load LTC operation in a 4-
cylinder turbo-charged research diesel engine, Han et al. [115]
found that PFI of butanol with diesel DI deteriorated the emission
performance of the engine due to early auto-ignition of butanol. A
low n-butanol ratio of 0.38 and a high EGR rate of 40% are required
to prevent this behavior. Chen et al. [128] studied the effects of
butanol concentration (0–65%) on combustion, performance and
emissions of a DI diesel engine under different EGR rates (0–45%)
using butanol PFI and diesel DI. It was observed that peak cylinder
pressure and HRR decreased with butanol concentration at high
EGR rates. With butanol PFI, HC and CO emissions escalated with
102 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
increased butanol concentration and affected engine performance
when compared to diesel/butanol blends. It was also shown that
butanol PFI coupled with diesel DI and EGR can simultaneously
reduce NOx and smoke emissions to very low level.
Liu et al. [132] injected n-butanol into the intake port and
soybean biodiesel directly into a single cylinder CRDI engine at a
constant speed of 1500 rpm. EGR rates between 35% and 45% were
used. The injection timing was adjusted to maintain a constant
50% burn-point. The effects of three pre-mixed ratios of 80%, 85%
and 90% at late and early injection timings were investigated. It
was found that NOx emissions were lower and soot emissions
remained constant at early injection when compared to late
injection. NOx and soot reduced simultaneously with increase in
both HC and CO emissions under increasing EGR rates. The ITE of
the engine got reduced by 1% to 2% when EGR is increased to 45%.
An experimental study regarding the combustion and emission
characteristics of a DI diesel engine operating under reactivity
controlled combustion ignition (RCCI) enabled by PFI of n-butanol
and DI of cottonseed biodiesel was conducted by Soloiu et al. [133]
at 5.5 bar IMEP and 1400 rpm. The results were compared to ULSD
2 and it was found that butanol addition resulted in simultaneous
reduction of NOx (35%) and soot (90%) emissions. Zhu et al. [134]
showed that the use of high butanol fraction coupled with high
EGR can produce better results in emissions and efficiency of a
modified single cylinder research engine that use a set of dual-
injection system which includes a CRDI for diesel and PFI for
butanol. The effects of various butanol proportions, EGR rates and
diesel injection timings were studied. The results specified that
increasing butanol fraction caused high HC and CO emissions
coupled with deteriorated engine performance. While there is a
massive reduction in smoke emissions, a slight increase in NOx
emissions is found with increasing butanol percentage. Increasing
EGR rates decreased NOx emissions but increased other regulated
emissions with a drop in engine performance. Advanced injection
improved performance and increased NOx emissions slightly with
a decrease in other regulated emissions.
Recently, Lopez et al. [130] acknowledged that butanol fumi-
gation can be attractive for meeting the current emissions stan-
dards. Their work investigated the effects of hydrous ethanol and
n-butanol fumigation on combustion, performance, emissions,
particle number concentration (PNC) and particle size distribution
in a 4-cylinder, turbo-charged automotive DI diesel engine. n-
butanol was found to be a better alternative for fumigation than
hydrous ethanol. Higher premixed combustion, low in-cylinder
temperature, faster combustion, lower performance, high THC and
CO emissions and low NOx and PM emissions are common fea-
tures between both alcohols. Nevertheless, butanol fumigation
showed better trade-off between PM and NOx þTHC than hydrous
ethanol when compared to ULSD. Butanol fumigation also reduced
the PNC and decreased the geometric mean diameter of particles.
Another recent study by Sahin et al. [129] compared the effects
of butanol/diesel blends and butanol fumigation of similar butanol
(2%, 4% and 6%) percentages on the performance, emissions and
heat release of a turbo-charged DI diesel engine. While smoke
emissions decreased significantly using both methods, the smoke
reduction ratio using fumigation was found to be higher than
blends. Similarly, NOx emissions generally decreased with fumi-
gation while it decreased for only 2% butanol/diesel blends. BSFC
increased for all butanol ratios with fumigation while it decreased
for 2% and 4% blends. The HRR is similar to neat diesel for blends
but fumigation presented double peaks (one earlier and one later
than neat diesel fuel).
3.4.2. Summary
Based on the literature review on butanol PFI coupled with
direct injection of diesel/biodiesel, the following information can
be inferred:
 While n-butanol/diesel blends have been attempted by upto
50% in volume in diesel engines [131], higher volume substitu-
tion of butanol is possible by upto 65% using dual-fuel injection
[128].
 Butanol PFI presented better trade-off between NOx/PM when
compared to butanol/diesel blends. NOx emissions are reduced
due to lower in-cylinder temperatures caused by butanol
evaporation. Lower smoke emissions are due to the oxygen
content in butanol.
 The combination of butanol-PFI and diesel-DI can change the
trade-off between NOx and smoke with a penalty in engine
performance. Massive reduction in smoke and NOx emissions
can be obtained when EGR is additionally used.
 Dual-fuel injection is a more effective strategy in reducing NOx
emissions when compared to the butanol/diesel blends
[129,131].
 High HC and CO emissions associated with deteriorated engine
performance is a common feature with butanol-PFI.
 The smoke reduction ratio with butanol-PFI is found to be
higher than butanol/diesel blends.
3.4.3. Future research directions
 Studies to improve engine performance under dual-fuel injec-
tion should be carried out. The optimum butanol-energy-share
with diesel that can deliver the best efficiency with low
emissions should be identified.
 Currently there are no studies investigating the use of water-
containing butanol which is more suitable for PFI operation.
3.5. Neat butanol operation in diesel engines
There are some difficulties in using neat butanol in conven-
tional diesel engines because of its lower cetane number, higher
latent heat of vaporization and higher resistance to auto-ignition
when compared to diesel. The following methods are employed to
utilize neat butanol in diesel engines,
 Port-injection of butanol and auto-ignition by preheated air
[135].
 Port-injection of butanol with high intake boost pressure (upto
1 bar gage) that shortens the ignition delay and facilities auto-
ignition [136].
 Direct high pressure injection of butanol, since the viscosity and
boiling point of butanol are suitable for high pressure injection
of 900 bar gage [115].
Stable ignition and combustion phasing can be controlled by the
use of high EGR rates, intake boost and multi-pulse injection
strategies [115]. The modifications that are required to accommo-
date butanol as a neat diesel engine fuel include the following,
 Installation of a port-fuel injection system consisting of
gasoline-type injectors, high pressure fuel-pumps, alcohol flow
meter and a separate tank for butanol storage. Butanol is less
hygroscopic and has high tolerance to water contamination;
hence it can be stored in fuel tanks for long duration without
corrosion problems [136].
 Plastic and rubber parts have to be replaced with alcohol tol-
erant materials, since n-butanol can corrode plastic parts and
can cause the rubber parts to swell over a period of time [53].
Table 6
Summary of investigations that studied the effects of butanol dual-fuel injection on performance and emission characteristics of various diesel engines.

Ref Engine Direct Injec- Butanol (B) PFI : EGR Test conditions Reference fuel Performance NOx Soot HC CO
tion : Fuel Intake Facto r

[131] 4S, DI diesel engine Diesel (D) 0–50% by volume No EGR Variable loads. Diesel BTE ▼ ▼ 73% at medium ▼ n/a n/a
loads.
[113] 1-cylinder, 4S, DI Peanut Two Fixed flow No EGR IMEP 1–3 bar, ULSD BSFC ▲ with ▼ 74% at IMEP ▼ 98% at IMEP ▲ ▲
diesel engine methyl ester rates: 0.4 Kg/h 800 rpm (Low butanol addition 3 bar 3 bar.
Biodiesel 0.6 Kg/h load and Idling BSFC 3 for all
(PME) speeds) fuels at
IMEP 3 bar.
Efficiency of

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
Butanol
PFI 4PME DI
[128] 6-cylinder, 4S, WC, Diesel (D) 0–65% by EGR rates 1900 rpm Diesel At 15% EGR with butanol with butanol with butanol with butanol
CR:16:1, heavy duty, concentration 0–45% IMEP 1.0 MPa HRR ▲ content. content. content. content.
CRDI diesel engine Close to Eur- PP ▲ with increasing with increasing ▲ with increas- ▲ with increas-
with a port fuel opean Sta- ID 3 EGR rates. EGR rates. ing EGR rates. ing EGR rates.
injection circuit. tionary Cycle At 45% EGR ▼ 17% at 45% EGR, ▼ 88% at 45%
(ESC) tests HRR ▼ 47% butanol EGR, 47%
B speed. PP ▼ butanol
ID ▲
ITE ▼
ISFC ▲ with buta-
nol content.
ISFC ▼ with
increasing
EGR rates.
[132] 1-cylinder, 4S, Soya bean Three premixed EGR rates 1500 rpm. Diesel ITE initially ▲ ▼ ▼ ▲ ▲
CR:16:1, WC, CRDI biodiesel (S) ratios of 80%, 85% 35–45% The injection and then ▼
diesel engine and 90% timings were ITE ▼ 0.6% at 90%
adjusted to premixed ratio.
keep the CA50)
[133] 1- cylinder, 4S, Cotton seed Fixed flow rates. Cooled EGR 5.5 bars IMEP ULSD#2 ID ▼ ▼ 35% ▼ 70% n/a n/a
RP:16.9KW, CR:16:1, biodiesel (C) at 1400 rpm
DI diesel engine
[134] Modified 1-cylinder, Diesel (D) Two butanol frac- EGR rates 15% 1400 rpm 0# Diesel ISFC ▲ with butanol with butanol with butanol with butanol
4S, CR:16:1, WC, tions of 20% and and 45%. IMEP – 1 MPa ITE ▼ content content content content
research, HD, DI, 40% (by vol.) Intake pressure with butanol con- with increase in with increase in with increase in with increase in
diesel engine – 0.18 MPa. tent and with EGR EGR EGR EGR
Injection tim- increase in EGR ▲ with advanced ▼ with advanced ▼ with advanced ▼ with advanced
ings at 5° CA ISFC ▼ injection timing injection timing injection timing injection timing
and 8° ITE ▲ with
CA BTDC advanced
injection timing
[130] 4-cylinder, 4S, Diesel (D) 10% of hydrous No EGR Mode ULSD BSFC ▲ 19.9% at ▼ at both M2 and ▼ at both M2 ▲ at both M2 ▲ at both M2
RP:59KW, CR:18.4:1, ethanol in M2 (95 Nm or low load M4 and M4 and M4 and M4
turbo- charged, DI energy basis 0.478 MPa of BTE ▼ 13.2% at
automotive diesel 10% of butanol in BMEP at low load
engine energy basis 2410 rpm) BTE 3 at
M4 (43 Nm or high load
0.216 MPa of
BMEP at
2410 rpm)

103
104 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115

▲ – increases; ▼ – decreases; 3 – no change; 4S – Four stroke; DI – Direct injection; CRDI– Common-rail direct injection; RP – Rated power; CR – Compression ratio; AC – Air-cooled; WC – Water-cooled; HD – Heavy duty; CA –
Crank angle; ATDC – Above top dead center; BTDC – before top dead center; LSD – Low sulfur diesel; ULSD – Ultralow sulfur diesel; HRR – Heat release rate; IMEP – Indicated mean effective pressure; BMEP – Brake mean effective
 A lubricity improver upto 500 ppm should be added to butanol,
since the lubricity of butanol is lower than diesel and can wear
down the moving parts of the engine and fuel system [136].
 A fuel-cooler needs to be installed in the high pressure pump to
keep the temperature of butanol down to avoid vaporization
n/a
CO

[136].
 An electrical heater, if preheated air is used for auto-igniting

pressure; BTE – Brake thermal efficiency; BSFC – Brake specific fuel consumption; CA50 – 50% burn-point; PP – Peak pressure; ID – Ignition delay; EGR – Exhaust gas recirculation; n/a – not available.
port injected butanol.

3.5.1. Combustion, performance and emission characteristics

Most of the research involving neat n-butanol usage in diesel
HC

engines has emerged very recently. A summary of investigations

that studied the performance and emission characteristics of die-
sel engines fueled with neat butanol is presented in Table 7. HCCI
combustion can reduce smoke and NOx emissions simultaneously
but its implementation in conventional diesel-fueled engines is
usually let down by uncontrollable ignition timing and early
Soot

combustion phasing which happens before the TDC that affects

▼

the engine efficiency. This is due to the high reactivity and low
at
▲ – increases; ▼ –
decreases; 3 – for

volatility of diesel. In these conditions, the use of less reactive and

highly volatile n-butanol can be favorable for HCCI operation. In
loads
for all loads
2000 rpm

4000 rpm

this regard, Maurya et al. [135] compared and tested gasoline and
n-butanol in one of the four cylinders of a DI diesel engine under a
all

high compression ratio (17.5:1) which is modified to operate in

NOx

HCCI mode. Combustion control methods like intake boost and

EGR were not employed in this study. Homogenous mixture of fuel
and air is prepared in the intake manifold using PFI. Auto-ignition
Reference fuel Performance

of this mixture is achieved by preheating the intake-air. The effect

of varying the intake air temperature and air/fuel ratio was
BSFC ▼

examined. It was found that HCCI operating range of butanol is

slightly smaller than gasoline. Also, butanol delivered lower ITE
and higher ISFC when compared to gasoline. Huge reduction in
NOx emissions with high HC and CO emissions was found in HCCI
mode. It was concluded that butanol has good HCCI characteristics
when compared to gasoline usage. This study does not take the
Variable loads Diesel

energy spent in preheating the air into consideration while cal-

culating the efficiency of the engine.
Variable loads
Test conditions

Neat Butanol can be a suitable candidate for LTC operation

at 2000 rpm.

at 4000 rpm.

because it can offer high resistance to auto-ignition, longer igni-

tion delay period and fast vaporization. A series of experimental
studies by a single research group recently explored the possibi-
lities of using neat butanol in a high compression ratio diesel
engine under various fuel injection strategies for improved emis-
sion performance and various intake dilution techniques to control
No EGR

combustion phasing [115,124,125,136–139].

EGR

Han et al. [115] explored the suitability and potentiality of neat

butanol for high-load LTC operation by carrying out tests in a 4-
of  2%,  4% and
Butanol (B) PFI :

cylinder DI diesel engine with a high compression ratio (18.2:1)

 6% by volume.
n-butanol ratios
Intake Facto r

using two strategies, viz. high pressure DI of butanol and butanol

PFI with a disabled pilot Diesel DI. It was found that n-butanol
showed promising potential under high pressure direct injection.
The soot emissions almost died out owing to the long ignition
delay and fuel-bound oxygen content of butanol. The stratified
Direct Injec-

butanol charge enabled LTC combustion between IMEP of 1 to

tion : Fuel

Diesel (D)

1.3 MPa and offered simultaneous reduction of NOx and soot

emissions with a moderate intake boost and EGR. On the other
hand, Butanol PFI with disabled pilot diesel DI resulted in ultralow
NOx and smoke emissions but required high EGR rates (51–57%) to
turbo-charged, CRDI

control the combustion phasing.

CR:18.25:1, WC,
[129] 4 cylinder, 4S,

Zheng et al. [137] considered the influence of intake boost and

diesel engine
Table 6 (continued )

EGR in phasing neat butanol combustion in a modified single

RP:48KW,
Engine

cylinder diesel engine with a high compression ratio (18.2:1).

Butanol-HCCI combustion required no use of dilution by EGR at
low/middle loads to achieve ultra-low NOx and soot emissions
which is not the case with diesel that depends on high intake
Ref

dilution for NOx reduction. EGR and intake boost is required at

 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
Table 7
Summary of investigations that used neat butanol in various diesel engines.

Ref Engine Fuel Test conditions Butanol Injection Intake Injection EGR Performance NOx Soot HC & CO
boost timing

[135] 4-cylinder, 4S, 652cc, HCCI n-butanol Intake air PFI and auto-igni-    ▼ ▼ No ▲
engine Ref: Gasoline temperature tion by preheated ITE Butanol oGasoline information
Air–fuel ratio (λ) air. ISFC Butanol 4Gasoline
[139, 124] 4-cylinder, 4S stroke, modified n-butanol 6.5 bar IMEP DI ✓ ✓ ✓ 3 at 6.5 bar IMEP at 6.5 bar IMEP. HC 3
to 1-cylinder CRDI diesel Ref: Diesel 1500 rpm at 8 bar IMEP ▼ Zero soot at CO ▼
engine Injection pressure ▼ to 0.2 g/KW h at high EGR rates.
– 900 bar high EGR rates
[138] 4-cylinder, 4S stroke, modified n-butanol 1500 rpm PFI ✓ ✓ ✓ EGR to reduce ROPR for ▼ ▼ ▲
to 1-cylinder CRDI diesel Ref: Diesel Injection pressure DI PFI and DI mode NOx DI4NOx PFI
engine – 90 MPa EGR PFI 4EGR DI
ITE DI4ITE PFI
[125] 4-cylinder, 4S stroke, modified n-butanol 6.5 bar IMEP Single-shot ✓ ✓  ▲ ▼ Near-Zero ▼ Near-Zero n/a
to 1-cylinder CRDI diesel Ref: Diesel 1500 rpm injection
engine Injection pressure Pilot-main ✓ ✓ ✓ ▲ moderate ▲ moderate ▲
– 600 bar injection
Two pilot – main ✓ ✓ ✓ ▼ ▼ ▼
injection
[137] FORD DURATORQ4-cylinder, n-butanol Low/middle loads Butanol –HCCI ✓   3 43–46% ▼ ▼ ▲
4S stroke, modified to Ref: Diesel - High loads ✓  ✓ ▼ ▼ ▲
1-cylinder CRDI diesel engine HCCI

▲ – increases; ▼ – decreases; 3 – no change; 4S – Four stroke; DI – Direct injection; CRDI– Common-rail direct injection; RP – Rated power; CR – Compression ratio; PFI – Port fuel injection; HCCI – Homogenous charge
compression ignition; IMEP – Indicated mean effective pressure; ROPR – Rate of pressure rise; EGR – Exhaust gas recirculation.

105
106 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
high loads to control high ROPR and combustion phasing. Butanol-
HCCI can improve the load range of the engine by 25% than diesel
HCCI. Intake boost has no effect on emissions at low/middle loads.
It was concluded that the low reactivity of butanol helped realiz-
ing optimum combustion phasing for achieving consistent diesel-
like efficiencies (43–46%).
In another study, Yanai et al. [138] used the same research
engine in the above study at a constant speed of 1500 rpm to
compare butanol-PFI and butanol-DI (at 90 MPa injection pres-
sure). The impact of intake boost, EGR and injection timing on
engine combustion, performance and emissions were considered.
The results showed that butanol-PFI required a very high EGR ratio
to control the ROPR while with butanol-DI, the ROPR can be easily
controlled to the same level by delaying the injection timing. Soot
and NOx emissions of both butanol-PFI and butanol-DI are com-
paratively lower than diesel-DI. NOx emissions of butanol-DI were
found to be slightly higher than butanol-PFI. Butanol-PFI pre-
sented lower ITE than butanol-DI with same NOx and ROPR in the
cylinder. In a similar study, Han et al. [124] used the same
experimental setup to perform engine tests at medium engine
loads (6–8 bar IMEP) to compare butanol and diesel employing a
single-shot injection strategy. The results indicated that neat
butanol combustion delivered comparable efficiency with lower
NOx and zero soot emissions with respect to diesel operation. It
was concluded that neat butanol require lesser EGR rates than
diesel to enable LTC operation with improved engine performance.
Recently, Zheng et al. [125] compared single-shot and multi-
pulse injection strategies for direct injection of neat butanol under
varying intake boost and EGR rates to enable LTC in the high
compression ratio engine used earlier. The engine was run upto
10 bar IMEP at a constant speed of 1500 rpm. The results are then
compared with baseline diesel DI. It was found that n-butanol
single-shot injection is more beneficial in terms of NOx and soot
emissions than diesel but provided very less room for combustion
control using injection timing. Use of EGR provides control over
combustion phasing to a certain extent but aggravates HC and CO
emissions. When the single-shot injection is split into pilot-main
injections, there is more room for combustion timing control but
NOx and soot emissions increase. When the single-shot injection
is split to two early pilot injections and a shortened main injection,
moderate amount of EGR is required to maintain combustion
control, low exhaust emissions and unaffected performance.
3.5.2. Summary
Based on the review of the available studies on neat butanol
usage, the salient points can be summarized as below:
 Simultaneous reduction of smoke and NOx emissions with
improved or un-effected engine efficiency is a common feature
of neat butanol usage in diesel engines.
 The less reactivity and high volatility of n-butanol is favorable
for controlling the ignition timing and combustion phasing and
eventually the implementation of HCCI operation.
 Butanol-HCCI vs. Gasoline-HCCI
Butanol has good HCCI characteristics when compared to
gasoline usage. However the operating range of butanol-HCCI is
slightly smaller than gasoline-HCCI. Butanol-HCCI shows lower
ITE and higher ISFC when compared to gasoline-HCCI. Massive
reductions in NOx emissions are obtained from Butanol-HCCI.
 Butanol-HCCI vs. Diesel-HCCI
Butanol-HCCI combustion required no use of dilution by EGR at
low/middle loads to achieve ultra-low NOx and soot emissions
which is not the case with diesel that depends on high intake
dilution for NOx reduction. EGR and intake boost are required at
high loads to control the high ROPR and combustion phasing for
high thermal efficiency. Butanol-HCCI can improve the load
range of the engine than diesel-HCCI.
 Butanol-DI vs. Butanol-PFI
n-butanol shows promising potential under high pressure direct
injection. Simultaneous reduction of NOx and soot emissions
can be realized with moderate intake boost and EGR. Butanol
PFI (with disabled diesel DI) results in ultralow NOx and smoke
emissions but requires high EGR rates to control the combustion
phasing. Butanol-PFI required a very high EGR ratio to control
the ROPR but with butanol-DI requires delay in the injection
timing to control the ROPR to the same level. NOx emissions of
butanol-DI are slightly higher than butanol-PFI. Butanol-PFI
presents lower ITE than butanol-DI when NOx and ROPR in
the cylinder is maintained constant.
 Butanol Single-shot vs. Butanol Multi-pulse
n-butanol single-shot injection is more beneficial in terms of
NOx and soot emissions than diesel but provided very less room
for combustion control using injection timing. Use of EGR provides
control over combustion phasing but worsens HC and CO emis-
sions. When the single-shot injection is split into pilot-main
injections, there is an increase in NOx and soot emissions. When
the single-shot injection is split to two early pilot injections and a
shortened main injection, moderate amount of EGR is required to
maintain combustion control, low exhaust emissions and unaf-
fected performance.
3.5.3. Future research directions
 Studies to optimize parameters like intake boost, EGR rates and
injection timing for effective control of combustion phasing and
ignition timing should be carried out. The best combination of
these parameters for low emissions with high improvements
should be identified using statistical methods.
 Majority of the studies involving neat butanol usage in diesel
engines have been carried out in single cylinder diesel engines.
Studies could be extended to neat butanol operation in multi-
cylinder engines.
 The use of EGR during neat butanol operation of engines can
cause carbon deposits and accelerated engine wear. Hence
studies regarding long-term engine durability of engines under
neat butanol operation are necessary.
4. Pentanol in diesel engines
Pentanol is a 5-carbon straight-chain alcohol that has greater
potential as a blending component with diesel fuel owing to its
higher energy density, higher cetane number, better blend stability
and less hygroscopic nature when compared to other widely-
studied lower alcohols like ethanol, methanol and even butanol.
Pentanol being a corrosion inhibitor doesn’t affect the fuel delivery
and supply systems unlike the case of methanol and ethanol [140].
Certain properties of pentanol like latent heat of vaporization,
density and viscosity are closer to diesel than other alcohols. This
can be deduced from Table 1. Pentanol is also an excellent
renewable alternative because it can be produced from biological
pathways like natural microbial fermentation using engineered
micro-organisms [140] and bio-synthesis from glucose using
Escherichia coli [141]. Pentanol being a longer-chain alcohol
requires lesser energy for its production when compared to other
lower alcohols [9].
The prospective use of pentanol as a new generation biofuel
attracted several researchers to conduct experimental and che-
mical kinetic modeling studies to analyze the fundamentals of n-
pentanol combustion which included information on its oxidation,
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
reactivity, laminar flame-speeds, flame instabilities, species con-
centration data and ignition delay times [142–147]. Tang et al.
[148] measured the ignition delay times of three C5 primary
alcohol isomers (n-pentanol, iso-pentanol and 2-methyl-1-buta-
nol) using a validated shock-tube facility and showed that the
ignition delay time and global activation energy decrease in the
order of iso-pentanol, 2-methyl-1-butanol and n-pentanol.
Pentanol diesel blends show better blend stability without
phase separation even after several days [149]. Though the visc-
osity of pentanol is very similar to diesel, pentanol/diesel blends
usually have lower viscosities than their pure components. This
could help achieving better atomization and combustion of pen-
tanol/diesel blends. It should be noted that pentanol/diesel blends
above 10% do not satisfy the lubricity requirements as per Eur-
opean EN 590 norms. The worst lubricity of pentanol/diesel blends
higher than 10% v/v is ascribed to the poor volatility of pentanol
which is unable to compensate for its lubricating capability [12].
From the safety perspective, pentanol/diesel blends have flash-
points above 37.8 °C and hence cannot be considered flammable.
The CFPP (Cold filter plugging point) properties of blends are also
within the EN 116 norms [15].
4.1. Combustion, performance and emission characteristics
Only a handful of studies have reported the use of pentanol in
diesel engines so far. Table 8 portrays the summary of investiga-
tions that utilized pentanol in diesel engines. Yang et al. [150]
studied the combustion characteristics of iso-pentanol in a HCCI
engine under wide ranges of speed, intake temperature, intake
pressure and equivalence ratio. Results are compared with the
data corresponding to that of gasoline and ethanol operation in
the same engine. It was found that iso-pentanol had higher reac-
tivity than gasoline and ethanol. Iso-pentanol showed an inter-
mediate temperature heat release (ITHR) comparable to gasoline
which is critical for maintaining combustion stability at high loads
without knocking. It was concluded that iso-pentanol can be used
in its neat form or as a blend with gasoline in HCCI engines.
Yoshimoto et al. [47] used pentanol as one of the eight oxy-
genates that have higher volatility and lower boiling points (which
include ethanol, 1-propanol, 1-butanol, 2-methoxyethanol,
2-ethoxyethanol, 2-butoxyethanol, and dibutyl ether) to improve
the viscosity and distillation characteristics of rapeseed oil. Blends
containing upto 33% v/v of oxygenates were used. Pentanol is
found to have good solubility with rapeseed oil. Addition of pen-
tanol has no effect on BSEC of the engine at high loads and smoke
emissions reduced linearly with increase in oxygen content of the
blend. NOx emissions remain unaffected.
The variations in engine performance and exhaust emissions of a
single cylinder DI diesel engine fueled with neem-oil/pentanol fuel
blends (5%, 10%, 15% and 20%) was assessed in comparison with neat
neem oil by Sivalakshmi et al. [43]. The BTE of the engine improved
and all the regulated emissions decreased with the addition of pen-
tanol. Campos-Fernandez et al. [15] studied the performance of a DI
diesel engine fueled with four pentanol/diesel blends (10%, 15%, 20%
and 25% v/v) and reported a slight loss of power, slight increase in
fuel consumption and better brake thermal efficiency. The study
concluded that pentanol/diesel blends upto 25% can be used safely in
diesel engines without any modifications.
Li et al. [151] studied the combustion and emission character-
istics of a diesel engine fueled with pentanol/diesel and pentanol/
biodiesel/diesel blends in a single cylinder DI diesel engine under
varying load conditions at constant engine speed of 1600 rpm.
Their results indicated that simultaneous reduction in soot and
NOx emissions occurred only at low and middle loads while NOx
emissions increased at high loads when compared to diesel fuel
operation. The indicated thermal efficiency was found to be higher
107
for all blends using pentanol. It was concluded that the bend
containing 40% diesel – 30% biodiesel – 30% pentanol is the best
for better combustion, emission and performance characteristics.
Wei et al. [152] examined the effect of using 10%, 20% and 30%
pentanol/diesel blends in a DI diesel engine and their results
showed that BSFC increased with increase in n-pentanol content in
diesel while the brake thermal efficiency remained unaffected.
They reported reductions in PM at all loads and 8% increase in NOx
emissions at high engine loads.
Li et al [153] investigated the combustion and emission char-
acteristics of a single cylinder DI diesel engine fueled with neat
pentanol under pilot-main and single-injection strategies and
concluded that simultaneous reduction of NOx and soot can be
achieved without EGR with neat pentanol operation with diesel-
like efficiency. High NOx emission at high engine loads has been a
common feature when pentanol is used in diesel engines. In-order
to address this issue, Rajesh et al [149] used cooled-EGR upto 30%
and mitigated NOx emissions by upto 30% at high load conditions
and 57% at low load conditions. This study concluded that penta-
nol/diesel blends can be used upto 45% in a diesel engine without
modifications and these blends when combined with medium EGR
rates can simultaneously reduce smoke and NOx emissions with a
little drop in engine performance.
Recently, Rajesh et al. [154] used 40% v/v of iso-butanol/diesel
and n-pentanol diesel blends to enable a partially premixed low
temperature combustion using low EGR rates and modified
injection timing in a single cylinder DI diesel engine. iso-butanol/
diesel blend exhibited better smoke suppression characteristics
than n-pentanol/diesel blends due to its longer ignition delay and
lower boiling point. Further, iso-butanol/diesel blends presented
superior EGR tolerance and better influence in overcoming the
NOx/smoke trade-off than n-pentanol/diesel blends which is
attributed to its highly oxygenated condition.
4.2. Summary
The few available studies on pentanol usage in diesel engines
indicate that pentanol can be blended upto 45% v/v in diesel and
can be safely used in diesel engine without any modifications and
without any damage. However, researchers have opined that long
term durability tests are required to recommend pentanol as a
straight diesel fuel. The combustion, performance and emission
characteristics of diesel engines using this alcohol can be sum-
marized as follows:
 The ignition delay prolonged with increase in pentanol content
in the blend due to the lower cetane number of pentanol.
Pentanol/diesel blends show higher peak cylinder pressure and
higher pre-mixed heat release rate compared to diesel.
 Pentanol/diesel fueled diesel engines generally offered diesel-
like or better thermal efficiency. This is due to the better
atomization and combustion of the blends as a result of its
lower viscosity (than diesel) and the oxygen content. However,
the BSFC of the engine is slightly lower due to the lower energy
content of pentanol/diesel blends (than diesel) thereby requir-
ing more amount of fuel to produce the same power output by
the engine.
 High NOx emissions are prevalent at high engine loads when
using pentanol/diesel blends. This is attributed to the dom-
inance of the high combustion temperature due to the oxygen
content and lower cetane number of pentanol blends over
temperature lowering effect caused by the higher latent heat of
vaporization of pentanol. However, these emissions can be
mitigated by using EGR.
 108
Table 8
Summary of investigations that used pentanol in diesel engines.

Ref Engine Fuel Test conditions/variables Blend Reference fuel Performance NOx Soot HC CO
designation

[47] 1-cylinder, DI diesel engine Rapeseed oil (RPO) – RPO100 RPO BSEC 3 3 ▼ n/a n/a
Rapeseed oil RPO67-P33 High load

B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
(RPO) þ ▲2-5%
Pentanol (P) Low loads
[43] 1-cylinder, 4S, RP: 4.4KW, Neem oil (NO) Variable loads, 1500 rpm. NO100 NO BTE highest for diesel. ▼ ▼ ▼ ▼
CR: 16.5:1, WC, DI diesel NO95-P5 BTE ▲ with increase in
engine NO90-P10 alcohol in blends.
NO85-P15 BSEC ▼ with increase in
NO80-P20 alcohol in blends.
[9] 3-cylinder, 4S, RP:34KW, Diesel (D)þ Variable loads, Variable D90-P10 Diesel BP 3 ▼ ▲ n/a n/a
CR:18.:1, WC, DI diesel Pentanol (P) speed. D85-P15 Torque 3
engine Diesel (D)þn- D80-P20 BTE ▲
butanol (B) D75-P25 BSFC
D70-P30 B25 ▼
D90-B10 B30 ▼
D85-B15 B 4P
D80-B20
D75-B25
D70-B30
[15] 3-cylinder, 4S, RP:34KW, Diesel (D) þPenta- Variable loads, Variable D90-P10 Diesel BTE ▲ ▼ ▲ n/a n/a
CR:18.:1, WC, DI diesel nol (P) speed. D85-P15 BP 3
engine D80-P20 Torque 3
D75-P25 BSFC 3
D70-P30
[152] 4-cylinder, 4S, RP:88KW, Diesel (D) þPenta- Variable loads, 1800 rpm. D80-P10 LSD BTE 3 high load ▼ high load high load
CR:19:1, DI diesel engine nol (P) D90-P20 BSFC ▲ ▼ low/ ▲ low/ ▲ low/
D80-P30 ID ▲ medium loads medium loads medium loads
Peak HRR ▲
[151] 1-cylinder, 4S, CR:16.7:1, Diesel (D)þ Variable loads, 1600 rpm. D70-BD30 0# Diesel ITE ▲ high loads ▼ ▼ ▼
CRDI diesel engine Biodiesel (BD) Double injection (Pilot- D70-P30 ISFC ▼ ▼ low/
Pentanol (P) main) D40-B30-P30 medium loads
[149] 1-cylinder, RP:4.7KW, Diesel (D) þPenta- Variable loads, 1500 rpm. D90-P10 Diesel ID ▲ ▼ ▼ ▲ ▲
CR:17.5:1, AC, DI diesel nol (P) D80-P20 BTE ▼
engine D70-P30 BSFC ▲
D55-P45
[153] 1-cylinder, 4S, CR:16.7:1, Neat Pentanol (P) IMEP 0.6 MPa. 1600 rpm. – 0# Diesel ITE ▲ ▼ ▼ ▲ ▲
WC, DI diesel engine Single and double injection ISFC ▼
strategy.

▲ – increases; ▼ – decreases; 3 – no change; 4S – Four stroke; DI – Direct injection; CRDI – Common-rail direct injection; RP – Rated power; CR – Compression ratio; AC – Air-cooled; WC – Water-cooled; LSD – Low sulfur diesel;
HRR – Heat release rate; BP – Brake power; ITE – Indicated thermal efficiency; ISFC – Indicated specific fuel consumption; IMEP – Indicated mean effective pressure; BTE – Brake thermal efficiency; BSFC – Brake specific fuel
consumption; BSEC – Brake specific energy consumption; PP – Peak pressure; ID – Ignition delay; EGR – Exhaust gas recirculation; n/a – not available.
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
 Soot emissions generally decreases with increasing pentanol
content in the blends as a result of its increasing oxygenated
nature.
 HC and CO emissions are usually higher.
4.3. Future research directions
 Long-term durability of diesel engines under pentanol opera-
tion should be carried out.
 The use of pentanol in advanced combustion strategies like LTC
and HCCI should be investigated.
 The emissions and performance of pentanol-driven diesel
engines should be investigated under transient conditions like
acceleration, load variations, starting or transient driving cycles.
 More research is required to investigate neat pentanol usage in
diesel engines. Particularly, high pressure pentanol direct igni-
tion can be attempted since the viscosity and boiling point of
pentanol are closer to diesel.
5. Other higher alcohols in diesel engines
Longer-chained straight chain alcohols with even number of car-
bon atoms and a single hydroxyl group attached to the terminal
carbon are classified as fatty alcohols [155]. An advantage of these
alcohols is that they require significantly lesser energy for their
production than lower alcohols like ethanol and methanol. This is
because the biological process used for their production can stop
breaking down the complex macromolecules much earlier. Hence a
relatively lesser energy investment is required for their production.
Majority of the studies involving this group of higher alcohols (hex-
anol and higher) in diesel engines used them as surfactants/solvents/
emulsifiers in very few percentages for improving the stability of
ethanol/diesel or methanol/diesel blends or emulsified fuels. A quick
look into the properties of higher alcohols beyond pentanol from
Table 1 indicates that they are very close to diesel. The application of
these alcohols as major blending components with diesel and their
subsequent use in diesel engines are gradually emerging. Table 9
provides the summary of experimental results related to use of other
higher alcohols above pentanol in diesel engines.
Hexanol is a six-carbon straight chain alcohol which is currently
produced by the oligomerization of ethylene [156]. Hexanol is used as
a surfactant in stabilizing diesel micro-emulsion [157], methanol-diesel
[158] and ethanol-diesel [159] emulsified fuels for use in CI engines. It
was shown in a study that n-hexanol can be converted into 1-hexene
which can selectively generate jet or diesel fuels [160]. Recently, Philips
et al. [161] engineered a sustainable pathway to consistently produce
hexanol by syngas fermentation using Clostridium carboxidivorans in a
low-cost medium. Kinetic modeling studies on hexanol oxidation and
combustion have been carried out in a jet-stirred reactor [162] and
opposed flow diffusion flame [163]. Experimental data on reaction
pathways, concentration profiles of reactants, stable intermediate
species, laminar flame speeds are available.
Sathiyagnanam et al. [164] used 10% of hexanol to increase the
blend proportion of ethanol in diesel by upto 45% in volume. It was
found that the hydrocarbon moieties of hexanol molecules
develop a strong bond with diesel fuel while the single oxygen
molecule forms a very strong bondage with the hydrogen of
ethanol. Four ethanol/diesel blends (15%, 25%, 35% and 45%) were
prepared in this fashion and were used in a single cylinder diesel
engine to study its effects on engine performance and emissions.
The blends presented decreased soot emissions and unchanged
NOx emissions when compared to diesel operation. The high
cetane number of hexanol made up for the lower energy content
of ethanol and contributed for the slight improvement in
109
performance of the engine. Sundar et al. [165] used hexanol with
an objective to replace diesel by upto 50%. Five hexanol/diesel
blends (10%, 20%, 30%, 40% and 50% v/v) were prepared and used
in a single cylinder DI diesel engine. There is an increase in engine
efficiency associated with high NOx emissions and decrease in
smoke emissions. The study further demonstrated that simulta-
neous reduction of smoke density and NOx emissions is possible
with the combined use of hexanol/diesel blends and hot EGR
without affecting engine efficiency.
Octanol is a eight-carbon, straight chain fatty alcohol which is
industrially produced by oligomerization of ethylene [156]. It is
popularly used as a surfactant in improving the phase stability of
ethanol/diesel blends [166–169], hybrid fuel micro-emulsions [170]
and diesel–oil micro emulsions [157,159]. Ever since n-octanol was
identified as a bio-derived fuel from ligno-cellulosic biomass [171],
studies that analyzed the basic combustion characteristics are
emerging [172,173]. A detailed kinetic model for n-octanol combus-
tion was carried out in a shock tube and a jet stirred reactor. Ignition
delay times and stable species concentration profiles were experi-
mentally obtained [172]. Kerschgens et al. [173] analyzed the effects
of fuel structure of three different C8 fuels, namely n-octanol, di-n-
buthyl ether, and n-octane with respect to diesel engine combustion.
The fuels were tested in a single cylinder diesel engine and it was
showed that very low soot emissions at nitrogen oxide emissions
within the Euro 6 regulation limits can be reached. It was found that
physical properties of the fuel have no significant effect on ignitability
of these fuels and stoichiometric mixture fraction is found to be the
only quantity that affects the reactivity of the mixture which occur-
red after a long ignition delay.
McCormick et al. [174] assessed the effect of soy bean methyl ester
(SME) and 1-octanol at 2% by wt of oxygen in a 2-stroke diesel DI
engine. It was found that SME reduced PM by 20 and increased NOx
by 2-3% while octanol simultaneously reduced PM by 12% and NOx
by 3%. The decrease in NOx emissions for octanol was attributed to its
lower boiling point compared to SME. Ishida et al. [175] used octanol
upto 4% by volume as a surfactant in bioethanol/diesel blends in a
premixed compression ignition engine under EGR and achieved
remarkable improvement in NOx/PM trade-off. Recently, Akhtar et al.
[176] proposed 1-octanol as a biofuel with diesel-like properties and
engineered a bio-synthetic pathway to extract it from Escherichia coli.
Zhang et al. [177] tested an octanol/diesel blend (30% v/v) under
European stationary cycle and reported its effects on performance
and emissions on a single cylinder heavy-duty diesel engine. The
engine delivered diesel-like efficiency with a slightly higher BSFC.
The engine produced lesser smoke, CO emissions and higher NOx
emissions when compared to its operation with diesel fuel. Deep
et al. [178] conducted an experimental study to evaluate and com-
pare the use of 1-octanol as a supplement to conventional diesel fuel
at different blend ratios (10%, 20% and 30% v/v) in a medium capacity
unmodified diesel engine. All regulated emissions showed an
increasing trend with increasing octanol content in the blend and the
engine efficiency is slightly affected.
Dodecanol is a twelve-carbon, straight chain fatty alcohol
which can be obtained from palm kernel naturally or by hydro-
genation of coconut-oil fatty acids or methyl esters [179]. It is
primarily used as a surfactant to improve the phase stability of
ethanol/diesel and methanol/diesel blends. The hydrophilic nature
of ethanol and methanol causes phase separation when mixed
with diesel. Murayama et al. [180] found dodecanol to be the best
among 10 different solvents to improve the stability of methanol/
diesel blends. In this regard, Bayraktar et al. [181] used dodecanol
(1% v/v) in three methanol/diesel blends (5%, 10% and 15% v/v) and
ran a single cylinder diesel engine successfully with improved
efficiency. They also suggested that dodecanol could be used only
in meager proportions in methanol/diesel blends because of its
high viscosity and high ignition temperature which can be can be
110 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115

unfavorable to fuel atomization and ignition [182]. Cheung et al.
[183] and Di et al. [184] used 1–1.5% v/v of dodecanol to prepare
four stable ethanol/diesel blends (6.1%, 12.2%, 18.2% and 24.2% v/v)
for use in a four-cylinder DI diesel engine and obtained diesel-like
efficiency with decreased particulate emissions.
Micro-emulsified diesel (MED) is a fire-resistant fuel that has the
capability to reduce its inflammability by self-extinguishing even at
temperatures slightly above its flash point. Chunhua et al. [185]
measured the combustion and explosion performance of MED with
various surfactants like monoethanolamine, n-pentanol, n-hexanol,
heptanol, octanol, and decanol. It was found that n-octanol improved
the flash-point of diesel compared to the other four alcohols. The
ranking of surfactants based on improvements in fire-resistant cap-
abilities of MED is: n-octanol4n-decanol4hexanol4pentanol4n-
heptanol. n-octanol was found to be the best surfactant to improve
the explosion suppression properties of MED.
Ramirez et al. [186] explored the feasibility of using phytol, a
biologically derived 20-carbon heavy alcohol as a blending com-
ponent with diesel (5%, 10% and 20% v/v) in a heavy-duty single
cylinder diesel engine. No changes in combustion phasing were
found using phytol/diesel blends hence the SOI was unaffected.
NOx and CO emissions were found to be similar to that of neat
diesel fuel. The engine efficiency using phytol/diesel blends is
comparable to that of diesel fuel.
Recently, Koivisto et al. [14] investigated the combustion
characteristics of 17 alcohol fuel molecules that included straight
chain, branched and unsaturated structure between C8 and C16
alcohols in a single cylinder research diesel engine and compared
their emissions with their corresponding hydrocarbons. The
results showed that alcohols have longer ignition delays than
alkanes. This implied enhanced premixed combustion phase
resulting in higher in-cylinder temperatures that increased NOx
emissions. The particle number concentration increased but the
particulate mass decreased with larger premixed phases. Further
ignition delay is prolonged when the hydroxyl group is moved
towards the center of the carbon chain. Higher degree of branch-
ing and unsaturation also resulted in longer ignition delays. The
results of this study may help in the development of future higher
alcohol biofuels with different molecular structures to obtain
desired ignition and emission characteristics.
5.1. Summary
Taken together, the results of the referenced studies involving
the use of other higher alcohols (hexanol and higher) in diesel
engines indicate that:
 Small quantities of these alcohols can be used to stabilize
methanol/diesel and ethanol/diesel blends. High blending pro-
portions of ethanol with diesel may be achieved by adding these
alcohols [164].
 Lesser energy investment is required for producing these alco-
hols when compared to ethanol and methanol. Sustainable
production by biosynthesis of these alcohols from biomass
feedstocks using engineered micro-organisms is underway to
ensure availability in substantial quantities.

Table 9
Summary of investigations that used other higher alcohols above pentanol in diesel engines.

Ref Engine Fuel Test conditions/ Blend Reference fuel Performance NOx Soot HC CO
variables designation

[165] 1-cylinder, Diesel (D)þ Peak load, D90-HX10 Diesel ID ▲ ▼ 60% ▼ n/a n/a
RP:5.2KW, CR: Hexanol (HX) 1500 rpm, 25% D80-HX20 PP 3 with EGR
17.5:1, AC, DI diesel EGR. D70-HX30 BSFC ▲
engine D60-HX40 BTE ▲
D50-HX50
[164] 1-cylinder, Diesel (D)þ Variable loads, D70-E20- Diesel BTE ▲ 1.89% ▲ at high ▼ ▲ n/a
RP:5.2KW, CR: Ethanol (E) 1500 rpm. HX10 D70-E20- loads D55-E35-
17.5:1, WC, DI die- Hexanol (HX) D65-E25- HX10 HX10
sel engine HX10 shows shows
D55-E35- highest BTE highest
HX10 PP ▲ reduction
D45-E45- HRR ▲
HX10
[174] 6-cylinder, 2S, Diesel (D)þ Heavy-duty In #2 Diesel n/a SME ▲ All ▼ 12- OCT ▲ 4% SME ▼
RP:275bhp, Soybean methyl transient test 2S engine 2% 15% SME ▼ 10% OCT ▼
turbo-charged, ester (SME) (CFR 40, Part 86, D99-SME1 SME ▲ SME ▼ OCT ▲ 25% SME ▼
inter-cooled, DI Diesel (D)þ Subpart N) D99-OCT1 2-3% 20% OCT ▼
engine Octanol (OCT) D99-E1 OCT ▼ OCT ▼
6-cylinder, 4S, Diesel (D)þ D99-DEC1 3% 12%
RP:345bhp, Ethanol (E) In
turbo-charged, Diesel (D)þ 4S engine
inter-cooled, DI Decanoic D99-OCT2
engine acid (DEC) D99-SME2
D99-E2
D99-DEC2
[178] Unmodified WC Diesel (D)þ Variable loads. D90-OCT10 Diesel BSFC 3 ▲ ▲ ▲ ▲
diesel engine Octanol (OCT) D80-OCT20 BTE ▼
D70-OCT30
D60-OCT40
[186] 1-cylinder, CR: Diesel (D)þ 1500 rpm, Injec- D95-PHY5 Diesel BSFC ▼ 3 n/a n/a 3
16.278:1. simulated Phytol (PHY) tion quantity – D90-PHY10
turbo-charged 100 mm3, Injec- D80-PHY20
research diesel tion timing.
engine

▲ – increases; ▼ – decreases; 3 – no change; 4S – Four stroke; DI – Direct injection; RP – Rated power; CR – Compression ratio; AC – Air-cooled; WC – Water-cooled; HRR –
Heat release rate; BTE – Brake thermal efficiency; BSFC – Brake specific fuel consumption; PP – Peak pressure; ID – Ignition delay; EGR – Exhaust gas recirculation; n/a – not
available.
 B. Rajesh Kumar, S. Saravanan / Renewable and Sustainable Energy Reviews 60 (2016) 84–115
 Smoke emissions are generally reduced due to the presence of
fuel-bound oxygen that assists combustion.
 NOx emissions are generally comparable to or higher than that
of neat diesel fuel depending on the balance between the effects
of higher heat of evaporation and lower cetane number of these
alcohols. This balance depends on the type of engine used and
its operating conditions [52].
 The efficiency of the engine is usually diesel-like or even better
but the BSFC is slightly affected due to the low energy content of
these alcohols.
 Octanol and Hexanol can replace diesel by upto 30% and 50% v/v
respectively. Dodecanol can be used upto 1.5% for obtaining
higher blends of ethanol/diesel. Phytol can be used only as a
blending agent by upto 20% but cannot be used in its neat form
in diesel engines.
5.2. Future research directions
 The future of utilizing these higher alcohols to partially or wholly
replace fossil diesel in diesel engines solely depends on the
development of bio-production technologies that can improve
their yield and cost-effective substrates to produce them.
6. Conclusions
Higher alcohols are second/third generation biofuels that can
be derived from ligno-cellulosic biomass using sustainable path-
ways without much any reliance on food crops. As typical biofuels,
they are capable of addressing the two-pronged issue of envir-
onmental degradation and energy insecurity. The following con-
clusions can be drawn after this extensive survey concerning the
use of 3-carbon propanol to 20-carbon phytol in diesel engines:
 Propanol can be used by upto 20% v/v, butanol by upto 40% v/v,
pentanol by upto 45% v/v, octanol by upto 30% v/v and hexanol
by upto 50% v/v as blending components with fossil diesel for
fueling diesel engines. However neat butanol and pentanol
operation is only possible using high pressure direct injection in
diesel engines. Phytol can be used only as a blending agent by
upto 20% v/v but cannot be used in its neat form in diesel
engines. So far dodecanol, decanol, heptanol were used in small
percentages by vol. with diesel, for stabilizing lower alcohol/
diesel blends in diesel engines and further research is required
to use them in higher percentages with diesel.
 Alcohol addition prolongs the ignition delay of the blend.
Higher alcohol/diesel blends show higher peak cylinder pres-
sures and higher pre-mixed heat release rates compared to
diesel. The longer the length of the carbon chain of the alcohol,
the more ignitable the alcohol is.
 BTE of the engine fueled with alcohols like propanol and
butanol generally showed improved performance due to the
higher percentage of premixed combustion as a result of low
cetane number of propanol and improved spray characteristics
due to decrease in viscosity and density of the blends. BTE drops
with the usage of pentanol and other higher alcohols in diesel
engines.
 BSFC of the engine usually suffers due to the lower energy
content of higher alcohols.
 Particulate emissions generally decrease due to the oxygenated
nature of higher alcohols. The longer the length of the carbon
chain of the alcohol, the lesser the oxygen percentage is.
However, higher alcohols upto pentanol can still enhance the
premixed combustion phase with their longer ignition delay
111
allowing sufficient mixing of air/fuel and also improve the dif-
fusion combustion phase.
 NOx emissions generally decreased with increasing propanol or
butanol contents in the blend. However, alcohols involving
pentanol and higher, increased NOx emissions linearly with
their content especially at high loads. This variation is due to the
difference in domination between the effects of higher heat of
vaporization and cetane number. This delicate balancing also
depended on the specific engine and its operating conditions.
 HC and CO emissions generally increased with higher alcohols.
 EGR is the most common NOx reduction technique used in
higher alcohol fueled engines followed by late injection. The
combination of high rates of EGR, lower cetane number higher
alcohols (like butanol, pentanol) and late injection timing can
enable LTC strategy in diesel engines. This advanced combustion
strategy reduced smoke and NOx emissions simultaneously
with improved efficiency.
 Longer chain fatty alcohols like hexanol, octanol and dodecanol
are popularly used as surfactants to stabilize lower alcohol/
diesel blends and diesel–oil micro-emulsions.
 Research on sustainable production of these higher alcohols by
biosynthesis from biomass feedstocks using genetically engi-
neered micro-organisms is ongoing. The encouraging point is
that these alcohols require lesser energy investment for produc-
tion these alcohols when compared to ethanol and methanol.
 Higher production costs are the chief impediments for high-
volume higher alcohol use in diesel engines at this juncture. The
chief thrust areas for higher alcohol production include devel-
oping mutant strains with higher yield, higher tolerance to toxic
inhibition and low-cost substrates for fermentation.
 Further work is required in specifying optimum blend-fuel
characteristics and ensuring long term durability of the engines
that utilize these fuels.
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