Renewable and Sustainable Energy Reviews 117 (2020) 109498

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Renewable and Sustainable Energy Reviews

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

A comprehensive review on preparation, characterization, and combustion

characteristics of microemulsion based hybrid biofuels
Himansh Kumar a, b, A.K. Sarma b, *, Pramod Kumar a
a
Mechanical Engineering Department, Dr B R Ambedkar NIT, Jalandhar, Punjab, India
b
Chemical Conversion Division, Sardar Swaran Singh-National Institute of BioEnergy, Kapurthala, Punjab, India

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

Keywords: In recent years the detrimental environmental impacts and concerns of emissions from ever-increasing loco­
Microemulsion-based hybrid biofuel motives have motivated the scientific community to search for alternative fuels based on renewable lipids, such
Surfactant as microemulsion based hybrid biofuels (MHBF). Emulsification or hybrid fuel preparation process is one of the
Microexplosion
simplest among the other biofuel production processes that do not require any chemical reaction or complex
Stability
CI engine performance
chemical handling process. This article specifically reviewed various routes for the preparation of MHBF from
renewable lipid (oil) sources. In other words, the exploration of the utility of vegetable oil for MHBF formulation,
physicochemical properties, comparison with biodiesel, biodiesel blends and petrodiesel, phase stability and
performance analysis of CI engine are the targeted focus of the article. This study has also focused on the effects
of various fuel components viz. surfactants, co-surfactants, etc., upon the physicochemical characteristics of
MHBF. The microexplosion phenomenon that describes the actual combustion has been illustrated. The stability
assurance of MHBF is directly influenced by the hydrophilic-lipophilic balance (HLB) value. The engine per­
formance parameters viz., brake specific fuel consumption, mechanical, volumetric and overall efficiency have
been reviewed and found that these values are comparable to the biodiesel blends with petrodiesel and pure
petrodiesel. Emissions reported by the various researcher, however, have a positive attribute with respect to SOx,
CO and NOx which are always lowest, while using MHBF in comparison to biodiesel and petrodiesel, in contrast
to large emissions of thermal NOx in biodiesel. Unburnt hydrocarbon (UHC) is however in the higher side than
biodiesel blends and petrodiesel which is manageable with increasing load. It can be ascertained from the review
that MHBF can eventually replace the other renewable liquid fuel formulation in due course of time for CI en­
gines in agro-farming machinery or even in heavy-duty vehicles attributed to the simplicity of preparation
process.

1. Introduction
Compression ignition (CI) engines are one of the most proficient and
dependable energy-producing devices used based on liquid fuels. In the
20th century, the CI engines were preferentially running with
petroleum-derived fuels attributed to the less consumption and low cost.
The most important challenge across the researchers worldwide is to
minimize the harmful emissions of IC engines as these impose hazardous
effects on human health directly or indirectly [1,2]. In continuation,
these combustion products (harmful emissions) such as carbon monox­
ide (CO), unburned hydrocarbon (UHC), oxides of nitrogen (NOx), ox­
ides of sulfur (SOx), suspended particulate matter (SPM) and aldehydes
create respiration and cardiovascular deceases in humans [2–4]. These
are also responsible for global warming, acid rain and climatic disorder
[5–7]. CI engine is the main contributors to such type of emissions, the
reason for both human health and detrimental environmental issues
[8–10]. CI engines are generally used in transportation, power genera­
tion, industrial applications, agricultural equipment and earth movers
[11,12]. CI engines emit approximately the entire range of harmful
emissions. Despite detrimental health consequences, these are exten­
sively used due to their high performance and low maintenance cost
[4–6].
Dr. Rudolf Diesel had demonstrated the first peanut oil-based CI
engine in 1893 [5,6]. Subsequently, countless researchers had reported
the use of vegetable oil as an alternative fuel for CI Engine. But, the
ample availability of petroleum products and its superior characteristics
created a barrier against the use of vegetable oil. Recently, due to new

* Corresponding author.
E-mail address: anil.sarma16@gov.in (A.K. Sarma).

https://doi.org/10.1016/j.rser.2019.109498
Received 8 February 2019; Received in revised form 1 October 2019; Accepted 15 October 2019
Available online 22 October 2019
1364-0321/© 2019 Published by Elsevier Ltd.
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Table of abbreviations/ nomenclatures

MHBF Microemulsion based hybrid biofuel

SVO straight vegetable oil
CI compression ignition
BTE brake thermal efficiency
BSFC brake specific fuel consumption
GCV gross calorific value
PCP peak cylinder pressure
NHRR net heat release rate
ID ignition delay
W/O water in oil
O/W oil in water
W/O/W water in oil in water
O/W/O oil in water in oil
Fig. 1. W/O type reverse micelle microemulsion.
HLB hydrophilic lipophilic balance
CO carbon monoxide
CO2 carbon dioxide environment to obtain fuel products like petrodiesel [9,10]. However,
UHC unburned hydrocarbon this method has certain drawbacks like uncontrolled reaction, undefined
NOx oxides of nitrogen product quality and post-treatment of end products, etc.
SO2 sulfur dioxide In hydroprocessing, renewable biocrude is formed from SVO with the
SPM suspended particulate matter help of high-pressure high-temperature reactor, in the presence of
hydrogen environment [12,13]. After that, this renewable biocrude is
distilled and different petroleum-like products are collected. Renewable
diesel, which is formed by this process has superior quality than petro­
inter-government regulations on harmful emissions after the Kyoto diesel but, the production cost confines its implementation [13–16].
Protocol (1991), Paris Convention (2015) and the rapid enervation of Nevertheless, the useable distilled liquid fuel fraction is reduced to less
global petroleum reserves promoted to develop an alternative fuel than 60% of the original HVO [13].
source which produced less pollution and renewable in nature into some Microemulsification technique is also popularly named as a viscosity
extent [13–16]. reduction technique [14–16]. It involves blending of two immiscible
Biofuel has the potential to overcome these environmental issues. liquids, a viscosity modifier (lower molecular weight alcohols) and
Biofuel can be synthesized through various preparation routes and it is a vegetable oil, biodiesel or vegetable oil/biodiesel-petrodiesel mixture.
possible aspirant of petrodiesel because of its comparable physico­ Surfactant and a co-surfactant are used to minimize the interfacial ten­
chemical and fuel properties [17–19]. Straight vegetable oil (SVO) sion in-between these two liquid films and to form a stable emulsion
which is a simple lipid, especially the non-edible oil is a potential [17–19]. In brief, microemulsions are an anisotropic, transparent and
feedstock due to its availability, renewable-nature and environmental thermodynamically stable mixture of oil in water (O/W) or water in oil
benefits [20–22]. But its high viscosity creates low injection pressure, (W/O) stabilized with the help of surface-active agents (surfactants/­
poor fuel atomization and prolong combustion as compared with pet­ co-surfactants) [20–22].
rodiesel [20,21]. Moreover, the low calorific value, high density and low P. A. Winsor had introduced four types of microemulsions i.e. Type I;
cetane number respite its direct use in CI engines. In summary, the major oil in water emulsion, Type II; water in oil emulsions (reverse micelle
issues with the use of straight vegetable oil are injector fouling, carbon microemulsion), Type III; bi-continuous middle phase emulsion and
deposits at injector orifices, stricken oil rings, gum formation and Type IV; single-phase isotropic emulsion [22–24]. But the current trend
decrement in lube oil life [8–11]. Therefore, the use of SVO is usually of interest is to study the water in oil (Type II) type reverse micelle-based
considered to be unacceptable and unworkable for CI engines [14–16]. microemulsion [23–25]. Fig. 1 depicts the structural entity of the W/O
To overcome these issues, caused by the physicochemical properties of type microemulsion.
SVO, different techniques are used i.e. mixing of SVO with petrodiesel, Microemulsion-based hybrid biofuel (MHBF) consists of water/
preheating before SVO injection, pyrolysis, transesterification, hydro­ ethanol (polar), vegetable oil (non-polar) and a surface-active agent
treatment of SVO and microemulsification of SVO with suitable surfac­ [23–26]. Very recently, the structural entity of a waste cooking oil-based
tant and viscosity modifier [5–10]. hybrid fuel was reported that calculated the approximate droplet using
A large volume of research articles has been reported and demon­ Abogado’s Nos [26,27]. This technique has many advantages such as no
strated that CI engine can be effectively run with biodiesel (trans­ by-products, very less production time and cost, least requirement of
esterification process) [8–10]. Biodiesel is a renewable, highly controlled environment and non-involvement of a chemical reaction.
oxygenated, non-toxic and environment-friendly fuel for CI engine [10]. Post-production neither requires a special vessel for storage and nor
Oxygenated characteristics of biodiesel result appropriate combustion engine modification during combustion and actual application [25–27].
with low SPM, CO and UHC but, produces higher NOx emissions due to Although MHBF has reported low gross calorific value (GCV), it creates
the high combustion temperature. It has reported by many researchers low in-combustion temperature due to the higher latent heat of vapor­
that biodiesel produced 10% higher NOx to that of petrodiesel [9–11]. ization of emulsified alcohols which results in a huge reduction in NOx,
The other techniques such as dilution (direct blending), pyrolysis, CO, smoke emissions and particulate matter [28–30].
hydrotreating and micro-emulsification have their own competitive Handful research on MHBFs has been conducted and very few review
merit/demerit attributed to its easy processing routes and high-quality articles were published on limited types of compositions, such as an
end products [10–14]. emulsion of petrodiesel, biodiesel and water/alcohols [26–32]. Also, in
Dilution (direct blending) of vegetable oil with petrodiesel is the the earlier review articles, microemulsion was prepared with using of
easiest method to reduce the viscosity of vegetable oil, but the problems petrodiesel and other non-renewable sources and its effects on CI engine
associated with the SVOs are always persisted [12–16]. In the pyrolysis performance were also reported [25–30]. But the current study is
method, vegetable oils are cracked thermally in a controlled air specially focussed upon the MHBF from renewable sources and to study

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H. Kumar et al.
its effects on CI engine performance, combustion, and emission. This
review paper has also focussed upon emulsion stability of different
combination of vegetable oils with petrodiesel, biodiesel and
surfactant/co-surfactant after the preparation phase. This review paper
has also explored the involvement of alcohol as a
surfactant/co-surfactant and its effect on fuel properties, combustion,
performance, and emission. Unlike other review papers, the present
review paper has specially emphasized upon the vegetable oil-based
MHBFs and its uses in CI engine, instead of another petrodiesel/bio­
diesel emulsion. This paper has suggested for conceivable research in
various renewable additives to rally the limitations of vegetable
oil-based MHBF.
2. Methodology
Microemulsion can be formulated from two types: O/W emulsion
and W/O emulsion. In the first type, oil acts as a dispersed phase and
water acts as a dispersed medium while in the second it is reversed
[30–34]. In MHBF formulation, water/ethanol/methanol (polar solvent)
and vegetable oil/biodiesel (non-polar) are mixed (immiscible liquids)
and formed a single-phase system with the help of surfactant (anionic,
non-ionic, cationic, Zwitterionic) [35–38]. MHBFs are isotropic and
thermodynamic stable in nature [39,40]. The droplet size of MHBFs lies
in the range of 10–150 nm [38–40].
2.1. Components of MHBF
MHBF is a multi-component fuel system in which generally three/
four components i.e. polar component (water/ethanol/methanol), non-
polar component (vegetable oil/biodiesel), surfactant (water-loving/
hating and oil-loving/hating) and a co-surfactant are used to form single
phase-stable fuel system through mixing in an appropriate ratio. Co-
surfactants are generally used to enhance the stability of MHBF [32,
38–40].
2.1.1. Polar components
Polar components (water/ethanol/methanol) are used as a viscosity
modifier to reduce the steric hindrance and increase the mobility that
reduces the viscosity of vegetable oil/biodiesel [33–35]. But, the excess
amount of water in MHBF resulted in low cold flow property and lowers
the GCV, which in turn reduces the engine efficiency and engine life
[36–38]. Also, the use of higher % of methanol is also limited due to its
highly reactive nature which can damage the engine components
[25–37]. Instead of this, ethanol contains a favourable calorific value,
good cold flow properties and higher latent heat of vaporization, which
promotes its use as a viscosity reduction component in MHBF [39,40].
2.1.2. Non-polar components
Vegetable oil from petrocrops, biodiesel, and oil from animal fat can
act as a non-polar component to form MHBF [30–33]. It generally
contains a long chain of hydrocarbon, which is the main component of
MHBF. Kinematic viscosity and acid value of these feedstocks play an
important role during the formulation of MHBF [33–35]. The kinematic
viscosity decides the concentration of viscosity reduction agent (solvent)
in MHBF and the acid value decides the preparation steps [36–38]. The
important fuel property i.e. GCV limits the concentration of viscosity
reducing agent in MHBF [38–40]. In this respect, less viscous oil feed­
stocks are preferably used to form MHBF that limits the concentration of
viscosity reducing agent in MHBF and maintain its GCV [32–35].
2.1.3. Surfactants/co-surfactants
Surfactant, also named as the surface-active agent is used to mini­
mize the interfacial tension in-between two liquid films [41–43]. There
is a long list of surface-active agents, used to form various types of
microemulsions, but the interest has focussed upon bio-based surfa­
ce-active agents due to its renewable nature, free from nitrogen, sulfur,
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Renewable and Sustainable Energy Reviews 117 (2020) 109498
Table 1
Various types of commercially used surfactant to form stable microemulsion.
Surfactant Hydrophilic-Lipophilic Ref.
Balance
Span80 (C24H44O6) 4.3 [43, 62,67,
74]
Span 83 (C66H126O16) 3.7 [29,30,42,43]
Span 20 (C18H34O6) 8.6 [23,24,45]
Span40 (C22H42O6) 6.7 [44,45]
Tween 80 (C64H124O26) 15 [46–48]
Tween 20 (C58H114O26) – [49,51]
Brij30 (C20H42O) 9.7 [52,53]
Oleic acid C18H34O2 1 [55–57]
Oleyl alcohol (C18H36O) – [59–61]
oleyl amine (C18H37N) – [45–47]
1-butanol/2-butanol 4 [38–40,71]
(C4H9OH)
and acids [42–45]. The recently reported bio-based surface-active
agents are sorbitan monooleate, alcohol ethoxylate (hydrophobic),
polyisobutylene succinic anhydride ester of monomethyl-capped poly­
ethylene glycol, glycerin, and polyethoxyester-based surfactants, 2-
ethyl-1-hexanol, oleyl alcohol and n-butanol [35–40]. Bora [38–41]
et al. has recommended that n-butanol can be used as a surfactant to
decrease the interfacial tension between polar and non-polar molecules.
The important property for selection of surface-active agents is its
hydrophilic-lipophilic balance (HLB) value.
The HLB value can be calculated using the following equation (1)
[38].
MH
HLB ¼ 20 � (1)
MH þ ML
where MH represents the molecular mass of the hydrophilic section and
ML represents the molecular mass of lipophilic section.
The HLB value of surfactant lies in the range of 0–20 and the degree
of variation shows its hydrophilic and lipophilic nature. The range of
HLB for W/O type emulsion is 3–6 and for O/W type emulsion is 8–16
[41–45]. The other HLB ranges surfactants are used in pharmacy, food
industries, and paint industries to prepare different types of emulsions
[46–48]. Some researchers have also reported the formation of micro­
emulsion from the mixture of two or three surfactants, however, the
bio-based MHBF surfactants are generally used solely [49–52]. Table 1
has shown about various types of commercial and non-commercial
surfactants, used to form stable emulsions are available in the litera­
ture. These surfactants are used solely or in combination to get optimum
HLB value.
2.2. MHBF preparation procedure
The most popular type of MHBF formulation is W/O type emulsion
[38–42]. Fig. 1 depicts the structural entity of a droplet of W/O type
emulsions. In this, the polar head (hydrophilic) of the surfactant is
directed towards the polar head of ethanol/water and the non-polar tail
(lipophilic) is slanted towards the non-polar tail of vegetable oil/­
biodiesel [40–43] forming Van Der Waals interactive bridge. The
blending or mixing of MHBF components can be processed using me­
chanical, electronic, magnetic and ultrasonic forces [51–55]. The blend
is considered to be microemulsion if it shows thermodynamically stable
nature, transparent, one component and droplet size is in the range of
10–150 nm [56–61]. A few researchers have also reported about oil in
water in oil (O/W/O) and water in oil in water (W/O/W) type multi
emulsions [37–62]. These types of formation are used to enhance the
stability of MHBF but these require non-bio-based surfactant to form a
stable emulsion and hence these are out of scope for this study. The
W/O/W and O/W/O type is the extension of W/O and O/W (also called
as multi-emulsion) type emulsion, used in medicinal and dairy products
[63–65] not generally as engine fuels. Fig. 2 shows about the P. A.
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

system so that it can be used in CI engine properly. Instability may

cause engine failure during operation and hence the stability of MHBF is
necessary to the extent of engine operation [63–66]. The instability of
MHBF depends on surfactant concentration, temperature, kinematic
viscosity, droplet size and foreign material present in the oil feedstock
[66–68]. Qi et al. [67] reported that the stability time is reciprocal with
the concentration of surfactant and co-surfactant. They had used Span
80 and ethanol as a surfactant and co-surfactant, respectively. Centrif­
ugal test is generally used to determine the effects of temperature
(thermal annealing) and gravitational forces upon the physical stability
of MHBF [68–70]. In this, the test sample is rotated at different speed
using centrifuge with a variation of temperature and monitored the
physical stability of MHBF. Physical observation is also used to figure
out the stability with respect to time. The HLB value of surfactant also
affects the stability of MHBF. The HLB value in the range of 3–6 is op­
timum for W/O type microemulsion [38–42]. Bora et al. [40–42] found
that the HLB value (4) of 1-butanol resulted in highest stability for the
MHBF with vegetable oil and ethanol. Kumar et al. [71] also found the
Fig. 2. P. A. Winsor I-II & IV type emulsion with W/O/W and O/W/ same results while 2-butanol was used as the surfactant.
O emulsion. Table 2 shows the different types of compositions and observation
parameters to form a stable microemulsion. From the comparative study
in Table 2, renewable and non-renewable types of microemulsions
Table 2 augment to understand the stability of different MHBF. Fig. 3 also de­
Various types of microemulsion composition and its stability duration. picts the approximate concentration of vegetable oil (non-polar)/
MHBF composition HLB Stability Time Stability/ Ref ethanol (polar)/surfactant to form different types of emulsions. At the
Measurement apex of the triangle, the concentration of the component is maximum
parameters
while on the face it is zero.
Vegetable oil n.r. Stable, except palm- Stable for 23 � C [15]
(canola, palm, diesel to 50 � C/25 � C
3. MHBF comparative analysis with B20, B100 and petrodiesel
algae)-diesel: microemulsion, for 30 min at
ethanol: solidify below 5000 rpm
surfactant-co- 6–6.5 � C. 3.1. Physicochemical properties analysis
surfactant
(different Stability of MHBF is one of the major concerns to be a single-phase
concentration)
system so that it can be used in CI engine properly. Instability may
Mesua ferrea L. Oil: 4 The sample is more Physical [39]
1-butanol: ethanol stable w.r.t. high examination, cause engine failure during operation and hence the stability of MHBF is
(60:30:10, concentration of centrifuge stress necessary to the extent of engine operation [63–66]. The instability of
60:20:20, surfactant (stable, test (7000 rpm MHBF depends on surfactant concentration, temperature, kinematic
30:50:20, 11 h, stable, 12 h). for 60 min)
viscosity, droplet size and foreign material present in the oil feedstock
30:40:30)
Bioethanol (5–25%)- – Stable with the Physical [72]
[66–68]. Qi et al. [67] reported that the stability time is reciprocal with
diesel (65–85%), addition of examination the concentration of surfactant and co-surfactant. They had used Span
pongamia pongamia biodiesel. 80 and ethanol as a surfactant and co-surfactant, respectively. Centrif­
biodiesel (10%) as ugal test is generally used to determine the effects of temperature
a surfactant
(thermal annealing) and gravitational forces upon the physical stability
Waste cooking oil: – Stable for two weeks n.r. [73]
ethanol-water: (70% WCO: 15% of MHBF [68–70]. In this, the test sample is rotated at different speed
surfactant water: 10% ethanol: using centrifuge with a variation of temperature and monitored the
(span80) 5% surfactant). physical stability of MHBF. Physical observation is also used to figure
Jatropha biodiesel 5 No water layer Physical [74]
out the stability with respect to time. The HLB value of Typical physi­
(JBD) with separation up to examination,
surfactant (S) 10% 48 h. homogenizer
cochemical properties for a range of MHBFs is shown in Table 3. Among
and water (W) (2000 and these emulsions, 60WBD30B10 E (60%, WBD -waste cooking oil-based
10% - 3000 rpm) biodiesel þ 30%, butanol þ 10%, ethanol) shows superior calorific
JBD10S10 W, value with acceptable viscosity [73]. This is due to the presence of
JBD10S15 W and
biodiesel in the emulsion [73]. The density and kinematic viscosity of
JBD10S20 W
Diesel: biodiesel: 11.67 (20 days, 20 days, Physical, [75] 60WBD30B10 E is higher than that of petrodiesel and other listed fuel
bioethanol 11 days) mechanical blends. Density and kinematic viscosity of MHBF depend upon the type
(80:15:5, homogenizer of surfactant and viscosity modifier [76–79]. MHBF with a higher con­
80:10:10, 80:5:15)
centration of alcohols shows comparable density and viscosity than that
n.r.: not reported. of petrodiesel [80–82]. The physicochemical properties of MHBF are
also depended upon chemical structure and carbon chain length of
Winsor I, II (W/O, O/W) and IV type of emulsion and about W/O/W and vegetable oils [38–42]. The long carbon chain length of vegetable oil
O/W/O type emulsions, used in food/medicinal/paint industries and shows relatively high GCV and high viscosity and vice-versa [83–85].
biofuel sector. The concentration of water in MHBF also effects on the physicochemical
properties, but, uncounted due to it is very less in quantity [86–88].
Similarly, due to the very low concentration of commercial surfactant,
2.3. MHBF stability concern the effect of surfactant is also of least interest [89–91]. Table 3 presents
the physicochemical properties, directly related to the concentration of
Stability of MHBF is one of the major concerns to be a single-phase vegetable oil, the amount of surfactant and viscosity modifier in ally.

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H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Fig. 3. Three-phase diagram to form various types of emulsions.

Table 3
Physicochemical properties of various types of MHBF.
Fuel components (vol %) & type Calorific Value (MJ/ Kinematic Viscosity Flash Point Cetane number/ Density (g/ Ref.
kg) (cSt) (� C) index cm3)

Petrodiesel (PD) 45.11 5.08 75 46 0.8365 [75]

Ethanol (E) 19.60 1.2 13.5 5–8 .788
n-Butanol (B) 29.20 2.54 – 25 .807
Crude coconut oil (CCO) 38.68 40.09 – – 0.9159
Virgin coconut oil (VCO) 38.82 39.49 – – 0.9174
85% VCOþ 10% ethanol (E)þ 5% butanol (B) (W/O 37.16 18.22 – – 0.9012
type)
67% VCOþ 17% Eþ 16% B 36.87 9.25 – – 0.8793
53% VCOþ 23% Eþ 24% B 36.09 6.20 – – 0.8631
87% CCOþ 10% Eþ 3% B 36.45 19.27 – – 0.9019
70% CCOþ 17% Eþ 13% B 35.83 10.15 – – 0.8816
54% CCOþ 23% Eþ 23% B 35.83 6.32 – – 0.8638
Soybean biodiesel (SBD) 38.81 7.8 166 52 0.8700 [79]
80% SBDþ 20% Eþ 31.29 – – – 0.8545
4 g Span80 þ .5% Water
80% SBDþ 20% Eþ 4 g Span80 þ 1% Water 31.28 – – – 0.8552
Waste cooking oil (WCO) 39.60 45 273 37 .880 [27]
70% WCOþ 15% Waterþ 10% Eþ .5% Span 80 – – – – –
Waste cooking oil biodiesel (WBD) 39.334 4.69 – – 0.887 [73]
60% WBDþ 30% Bþ 10% E 39.01 5.23 – – .907
50% WBDþ 40% Bþ 10% E 38.87 4.37 -. – .841
Jatropha curcas oil (JCO) 39.45 6.09 112 – .894 [71]
52% JCOþ 33% Bþ 15% E 37.81 6.72 – – 0.869
54% JCOþ 35% Bþ 11% E 38.34 5.95 – – 0.871
55% JCOþ 33% Bþ 12% E 38.25 5.91 37 – .870
60% JCOþ 30% Bþ 10% E n.r. 7.32 – – 0.891
Mesua ferrea L. seed oil (MSO) 38.83 20.52 – – .935 [38]
30% MSOþ 50% Bþ 20% E 36.76 3.92 – – .802
30% MSOþ 60% Bþ 10% E 36.16 4.99 – – .829
40% MSOþ 40% Bþ 10% E 37.42 5.20 – – .860
40% MSOþ 50% Bþ 10% E 37 5.66 – – .858
50% MSOþ 40% Bþ 10% E 37.24 8.93 – – .828
70% PD þ 20% rapeseed oil þ 10% B 41.27 3.85 49.55 0.84 [71]
Waste cooking oil (WCO) [67]
68% WCOþ19% Eþ13% B 37.62 7.21 43 35 .869
58% WCOþ25% Eþ17% B 35.81 5.36 39 32 .856

The effects of physicochemical properties as mentioned in Table 3
viz. calorific value, density, kinematic viscosity, flash point, cetane
number/index are the main aspect, as the CI engine performance,
combustion and emissions are directly linked with these. Singh [75]
et al. observed that the MHBF consisted of virgin coconut oil (85%),
ethanol (10%) and butanol (5%) shows maximum GCV than other pre­
pared blends, however, the effects of the said MHBF on BSFC of CI en­
gine was detrimental (higher) to petrodiesel. This happened due to the
high viscosity and low GCV of MHBF (as compared with petrodiesel),
which resulted in poor injection and finally led to incomplete

5
H. Kumar et al.
Fig. 4. Variation in BSFC for MHBF with respect to load [71,75].
Fig. 5. Variation in BSFC for MHBFs with respect to load [75,79].
combustion with higher MHBF consumption. On the other face, MHBF,
prepared from virgin coconut oil (53%), ethanol (23%) and butanol
(24%) showed lowest GCV among other test fuels also lower BSFC which
attributed to its low viscosity and this resulted from complete combus­
tion [75], wherein the BTE was highest among other test blends due to
proper combustion. The same trend was observed by Kumar et al. [71]
with MHBF from Jatropha curcas oil (55%), butanol (33%) and ethanol
(12%) and from among other fuel blends, the tested MHBF had shown
lowest viscosity. Also, the tested MHBF had comparable BTE to petro­
diesel but the BSFC was slightly higher than petrodiesel which was
found to be nearly similar to Jatropha biodiesel.
Qi et al. [68] had reported that the BSFC of the CI engine was pri­
marily depended upon the viscosity of MHBF. Nonetheless, MHBF with
higher GCV and lower viscosity was a suitable aspirant for CI engine use
as an alternative fuel [91–93]. The CN of MHBF was found to be
comparatively lower than petrodiesel and the same could be improved
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Renewable and Sustainable Energy Reviews 117 (2020) 109498
by using various additives [94–96]. In continuation with, Bora et al. [38]
had again reported the same trend with vegetable oil (Masua ferrea L.
oil), ethanol and butanol.
Though, the physicochemical properties of MHBF are directly
influenced by the concentration of viscosity modifier and surfactant,
which is also reflected in Table 3. Also, the higher concentration of
viscosity modifier and surfactant decreases the GCV of MHBF. Further­
more, at a lower concentration of viscosity modifier and surfactants,
there is no change of GCV in MHBF favoring the suitability of the
composition.
3.2. CI engine performance analysis
The performance of a CI engine depends upon the components of
injected fuel (MHBF). MHBF shows unique characteristics due to its
multi-component composition. Figs. 4 and 5 has shown the variation in
H. Kumar et al.
Fig. 6. Variation in BTE for MHBFs with respect to load [27,71,75].
brake specific fuel consumption (BSFC) for MHBF in respect of biodiesel
and petrodiesel. Kumar, Singh and Singh et al. [71,75,77] have depicted
that the BSFC shows comparable and sometimes higher trend than
biodiesel but always higher than petrodiesel. This is because of low GCV
and comparatively high viscosity of MHBF w. r. t. petrodiesel. In
contrast to biodiesel, MHBF results, proper combustion at full load
condition which is attributed to microexplosion of alcoholic contents
[96–99] although the GCV of MHBF becomes always lower.
Singh and Qi et al. [75,79] also reported the same trend. However, Qi
et al. [79] prepared biodiesel-based MHBF from ethanol, water (0.5–1%)
and non-renewable surfactant (Span 80) and reported that ethanol could
be used as a viscosity modifier and found equivalent BSFC with biodiesel
(Fig. 5). This was because of alcoholic contents in MHBF that scattered
at low temperature, which resulted in proper mixing of the encapsulated
oil film and air, hence efficient combustion [100–103].
The carbon chain length of oil feedstock and the concentration of
MHBF components reportedly played a major role in the performance of
CI engine due to its direct relation with fuel properties (GCV and vis­
cosity) [49–51]. Lesser BSFC was observed with long carbon chain
length oil feedstock based MHBF and vice versa [57–59]. The same was
observed through various researchers who have prepared MHBF from
water/ethanol/methanol, petrodiesel, biodiesel along with commercial
surfactant [65–68].
An experimental work with ethanol (polar) in vegetable oil (non-
polar) emulsion using butanol as a surfactant was reported by Kumar,
Singh and Singh et. al. [71,73,77]. Jatropha curcas oil (JCO) [71], crude
and virgin coconut oil (CCO & VCO) [49] and waste cooking oil (WCO)
[52] respectively, were used as a non-polar substrate to form stable
MHBF. The following Fig. 6 has shown the variation in brake thermal
efficiency (BTE) of CI Engine for various MHBFs and compare with its
B100 and petrodiesel. The results have shown that the BTE for JCO and
WCO based MHBF is almost comparable with its B100 and petrodiesel
and sometimes higher than petrodiesel except at part load for JCO based
MHBF. Singh et al. [49] also reported that VCO based MHBF had higher
BTE at all load conditions as compared with CCO based MHBF. This is
because of comparatively low viscosity of VCO based MHBF which
creates proper atomization during the start of combustion. Moreover,
the lighter molecules of added alcohols burnt earlier which results in
microexplosion and this promotes fast flame propagation of heavier
molecules of MHBF, resulting in proper combustion [97–99,104,105].
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Renewable and Sustainable Energy Reviews 117 (2020) 109498
It was reported by some researchers that water in MHBF also pro­
motes the combustion efficiency up to a certain level due to its internal
oxygen molecules [79,83,85,86,101–106]. Furthermore, an external
surfactant was required to form a stable emulsion with water [90,
93–96]. It has been also observed that without water MHBF shows better
results in comparison with water added MHBF because water reduces
the amount of free oxygen to the emulsion [61,62,66–70].
Microexplosion during combustion of MHBF has also an agreement
with the performance of CI engine because the gas pressure of the fuel-
air mixture at appropriate top dead center (TDC) decides its perfor­
mance and emission as reported in some literature [52,58,59]. Fuel
viscosity and calorific value have a direct relation with the micro­
explosion phenomenon of MHBF [38–42]. Microexplosion phenomenon
of MHBF has briefly discussed in combustion analysis section (3.3). The
following Table 4 has shown the effects of MHBF of CI engine perfor­
mance with proper reasoning.
It has been observed from Table 4 that the indicated thermal effi­
ciency (ηite) and mechanical efficiency (ηmech) of CI engine fuelled with
MHBF showed similar results to biodiesel [71]. Moreover, the BTE and
BSFC were nearly identical to biodiesel. The performance of MHBF has
always found to be lower than petrodiesel. This has associated with one
or many reasons such as low GCV, high viscosity, and low CN. Never­
theless, MHBF has shown acceptable results due to microexplosion
phenomenon. In addition, it has been reported by Singh, Kumar and Qi
et al. [71,75,77,80], that the variation in fuel properties of MHBF
imprint upon the performance of CI engine. Hence it can be presumed
that by regulating these properties one can find the best composition of
MHBF as per the requirement of CI engine.
3.3. CI engine combustion analysis
It has been reported that MHBF shows prolong combustion due to the
higher latent heat of vaporization of its alcohols at low and medium load
conditions in CI engines [62–65]. However, at full load condition, this
duration becomes short due to high in-cylinder temperature [66–68].
Microexplosion and high latent heat of vaporization of MHBF play a
major role during combustion as reported [68–70,78]. Microexplosion
phenomenon has concerned with reverse micelle microemulsion, in
which polar component (alcohol/water) surrounds from non-polar
component (vegetable oil/biodiesel) with the help of surfactant
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Table 4 Table 4 (continued )

Performance analysis of CI engine fuelled with MHBF. S. Composition Engine Engine Reasoning Ref.
S. Composition Engine Engine Reasoning Ref. No of the MHBF operating Performance
No of the MHBF operating Performance conditions parameters
conditions parameters
WCOþ25% 110, stroke medium load condition the
1 85% Virgin Single Brake This is due to [75] Eþ17% B (2) vol-661 cc, conditions same get
coconut oil cylinder, thermal high density and RPM-1500, and MHBF (2) reversed.
(VCO)þ 10% direct efficiency viscosity of P-3.5 kW @ shows Vegetable oil is
ethanol (E)þ injection, P- (BTE): MHBF along 1500 RPM. comparable highly viscous
5% butanol 3.8, constant Slightly lower with higher Engine was BTE at the component of
(B) rpm. Engine than reaction activity operated at same MHBF and do
87% Crude was operated petrodiesel. of ethanol in varying load condition but, not break at full
coconut oil at varying Brake specific MHBF. of 0%, 20%, the both show load condition
(CCO) þ 10% load (0%, fuel This is due to 40%, 60%, lower BTE at due to short
Eþ 3% B 30%, 56%, consumption low calorific 80% and full load combustion
86% and (BSFC): value of MHBF 100% of full condition to duration and
100%) at Higher than which is also load at that of this results
constant petrodiesel. depends upon constant petrodiesel inappropriate
rpm. Brake specific the rpm. and biodiesel. combustion.
fuel concentration BSFC: Lower This is due to
consumption (viscosity) of at low and low GCV of
(BSFC): ethanol and medium load hybrid fuel
Higher than butanol. condition for components
petrodiesel. MHBF (1) and which results
2 80% Soybean Single BTE: n.r. This is due to [70] MHBF (2) but higher
biodiesel cylinder, BSFC: micro-explosion at full load consumption at
(SBD) þ 20% compression Comparable of water, which condition the full load
Eþ 4 g ratio (CR) to B100. results proper same get condition to get
Span80 þ 16.5:1, mixing. reversed w.r. the same power.
.5% Water power- t. petrodiesel
(W), 1% W 11.03 kW and biodiesel.
@2000 rpm.
n.r.: not reported.
3 70% Waste Single BTE: Higher This is due to [27]
cooking oil Cylinder, CR than biodiesel micro-explosion
(WCO) þ 16:1, P- and lower of ethanol,
15% Waterþ 3.7 kW@ than which results
10% Eþ .5% 1500 rpm, petrodiesel proper
Span 80 vol- 630 cc BSFC: n.r. combustion.
4 55% Single BSFC: The is due to [71]
Jatropha cylinder, CR- Comparable lower viscosity
curcas oil 17.5, B- to B100 and of MHBF. Also,
(JCO) þ 33% 87.5 mm, S- higher than the higher
Bþ 12% E 110, stroke petrodiesel. reaction activity
vol-661 cc, BTE: of ethanol
RPM-1500, Comparable results proper
P-3.5 kW @ with B100 mixing of air
1500 RPM. and higher and fuel, hence
Engine was than appropriate
operated at petrodiesel. combustion.
varying load Mechanical This is due to
of 0%, 20%, efficiency: low calorific
40%, 60%, Higher than value of MHBF
80% and B100 and which is also
100% of full lower than depends upon
load at B20 and the
constant petrodiesel. concentration of
rpm. Indicated ethanol and
thermal butanol. Fig. 7. Pictorial view of microexplosion phenomenon and other stages of
efficiency: The is due to combustion for MHBF.
Higher than low viscosity of
B100, MHBF along
(Fig. 1). With the increase of cylinder temperature, the polar component
comparable with micro-
with B20 and explosion in
of MHBF vaporizes and break the encapsulation of micro-droplets,
lower than MHBF during which results in microexplosion [71–73]. Due to microexplosion,
petrodiesel. combustion. proper mixing of air and MHBF has occurred in the combustion chamber
This is the result and this helps in burning of heavier molecules of vegetable oil. Fig. 7
of improved in-
depicts the microexplosion phenomenon and other combustion stages
cylinder
combustion during combustion of MHBF.
attributed to The higher latent heat of vaporization of alcohols in MHBF has a
microexplosion direct impact upon CI engine combustion because this lowers the com­
of MHBF during
bustion temperature at all load conditions, as reported in the literature
combustion.
5 68% Single BTE: MHBF This is due to [27]
[66–70]. At no-load condition, the in-cylinder temperature becomes
WCOþ19% cylinder, CR- (1) shows appropriate lower than at part load and full load condition which resulted in prolong
Eþ13% B (1) 17.5, B- higher BTE at combustion but, ignition delay [80–84]. But at the same time at part load and full load
58% 87.5 mm, S- low to at full load conditions, lower NOx emissions were observed [48,70–72]. This has an
agreement with the higher latent heat of vaporization of alcohols in

8
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Fig. 8. Variation in cylinder pressure rate w.r.t. crank angle for MHBFs [27,71].

Fig. 9. Variation in Net heat release rate w.r.t. crank angle for MHBFs [27,71].

MHBF.
The following Figs. 8 and 9 have shown the effect of different hybrid
biofuels on peak cylinder pressure (PCP) and net heat release rate
(NHRR), in comparison with biodiesel and petrodiesel. It has been
observed from Fig. 8 that, PCP of MHBFs is always higher than petro­
diesel and comparable with biodiesel [49–52]. This was attributed to the
microexplosion of MHBF, which resulted in appropriate combustion
with higher PCP to other tested fuels [74–76]. However, it was reported
that the combustion peaks for MHBFs shift towards the TDC in com­
parison with petrodiesel and biodiesel [80–82]. This was attributed to
the late start of combustion and rate of pressure rise, the reason of low
cetane index and prolong combustion duration as compared with
petrodiesel and biodiesel. Qi et. al. [79]. have reported comparable PCP
to that of biodiesel with negligible effects of water in MHBF combustion.
The crank angle (� CA) for highest PCP (Fig. 8) among all MHBFs has also
varied due to different compositions of MHBF. This can be directly
correlated with the brief composition of MHBFs, mentioned in Table 3.
The following Table 5 has shown the effect of MHBF on peak cylinder
pressure (PCP), rate of pressure rise (ROPR), neat heat release rate
(NHRR), ignition delay (ID) and variation in combustion duration in CI
engine. However, combustion can be improved by shortening the igni­
tion delay. Further research is however required to overcome this
problem with MHBF.
Appropriate combustion in CI engine depends upon burning of

9
H. Kumar et al.
Table 5
Combustion characteristics of CI engine for tested fuel.
Engine Experimental Results
Combustion
parameters
Peak cylinder MHBF shows similar PCP in
pressure (PCP) comparison with B100. PCP
also shows the same crank
angle but slightly lower in all
load conditions [79].
MHBF shows almost
identical PCP with
petrodiesel at maximum
brake mean effective
pressure (BMEP) [81].
MHBF shows higher PCP
than B20, B100 and
petrodiesel at full load
condition with similar crank
angle position [71].
MHBF shows highest PCP
among petrodiesel and
biodiesel blends [62].
Rate of pressure MHBF shows Lower value at
rise (ROPR) medium load and higher
value at full load with that of
B100 [79].
MHBF shows lower value
than petrodiesel at maximum
BMEP [67].
The ROPR of MHBF shows
earlier start at part load and
late start at full load
compared to petrodiesel and
biodiesel blends [62].
Net heat release MHBF shows similar trend
rate (NHRR) but, lower and delayed to the
starting position of B100 at
all load conditions [67].
MHBF shows similar trend
with higher value to that of
B20, B100 and petrodiesel
[71].
The trend is higher but,
delayed at TDC w.r.t.
biodiesel blends and
petrodiesel [62].
Ignition delay MHBF shows prolong ID with
(ID) that of B100 and petrodiesel
[79].
MHBD shows prolong
ignition delay to that of
biodiesel blends and
petrodiesel [62].
Variation in The combustion duration for
combustion MHBF is short to that of B100
duration and petrodiesel at maximum
BMEP [79].
The combustion duration for
MHBF is short to that of
biodiesel and petrodiesel at
Possible Explanation
This is due to the prolong
ignition delay which increases
ignition delay due to low in-
cylinder temperature.
This is due to higher premixed
burning rate because of longer
ignition delay (ID).
This is because of
microexplosion phenomenon
which results proper
combustion of MHBF.
This is because of
microexplosion phenomenon
which results proper
combustion of hybrid fuels.
At medium load, very less
amount of MHBF is injected in
to the combustion chamber
and burning starts near top
dead center (TDC) so that the
premixed burning phase
expands up to the power
stroke which results less ROPR
to B100. But, at full load
condition, the ignition delay is
slightly longer than B100 and
hence more fuel accumulates
and at the same time water
drops improves the spray
atomization which results
quicker combustion and ROPR
tends to higher with B100.
Due to less cetane number of
MHBF which results prolong
ID.
This is due to low cetane index
and short combustion
duration.
Higher latent heat of
vaporization of alcohol is
attributed to the proper
mixing of MHBF and air.
This is because of proper air
fuel mixing of MHBF due to
higher latent heat of
vaporization.
This is due to prolong ID, low
cetane index and higher latent
heat of vaporization of
alcohols in MHBFs.
This is due to the addition of
ethanol and water which
shows higher latent heat of
evaporation and this decrease
in-cylinder temperature
during combustion.
This is the result of high
viscosity, low cetane index and
higher latent heat of
vaporization of alcohols in
hybrid fuels.
This is because of rapid
burning rate of ethanol which
promoted the combustion and
shortened the combustion
duration.
This is because of highly
volatile components in hybrid
fuels which improved
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Renewable and Sustainable Energy Reviews 117 (2020) 109498
Table 5 (continued )
Engine Experimental Results Possible Explanation
Combustion
parameters
part load and full load atomization during
condition [62]. combustion.
Cumulative heat The MHBF shows higher This is due to high viscosity,
release rate CHRR at part load and full low cetane index and low GCV
(CHRR) load condition than that of of hybrid fuels which in turn
petrodiesel and biodiesel results incomplete combustion
blends [62]. hence higher CHRR has been
observed.
injected fuel at few degrees before TDC but in case of alternative fuel,
proper combustion depends upon ignition delay related to the chemical
as well as physical properties of MHBF [75–77]. This combustion delay
was also reported with MHBF, which was due to high latent heat of
vaporization of alcohols at low and part load conditions [80–82]. But the
same was overcame at full load due to high in-cylinder temperature in
the engine [83–85]. From Table 5, it is evident that complete combus­
tion in CI engine depends upon precise fuel injection timing as well as
fuel’s physicochemical properties. As MHBF is a multi-component fuel
system, the physicochemical properties depend upon the concentration
of components as well as its effect on injection timing. Furthermore,
higher latent heat of vaporization is the main cause of prolonging
combustion with MHBF. It is observed that all combustion parameters
are depended upon the components of MHBF as clearly described in
Table 5.
It was reported that [58,67] the PCPs were identical with B100 and
petrodiesel, but at the same time higher PCP was reported with B100
and petrodiesel as shown in Fig. 10 [70–72]. Similarly, NHRR has
delayed but higher value with B100 and petrodiesel (Fig. 9), although
some of the authors [55,64] reported delayed and lower NHRR with
B100. This is simply because they used water in the formation of MHBF
[68,70]. Therefore, the combustion characteristics of any CI engine can
be regulated depending upon the components of MHBF and different
additives may also be tried to enhance the combustion quality of MHBF
in CI engine.
3.4. CI engine emission analysis
Reduction in CI engine emissions is the major attribute of alternative
fuels like MHBF. During combustion in MHBF, the microexplosion of the
encapsulated molecule of ethanol burst quicker and helps in proper
mixing of MHBF and air during the start of combustion [ 51–55]. The
high latent heat of vaporization of alcohols in MHBF also helps in drastic
reduction in oxides of nitrogen (NOx) emission during in-cylinder
combustion [62,71,75]. Reduction in other harmful pollutants such as
carbon monoxide (CO), smoke opacity and carbon dioxide (CO2) (de­
pends upon carbon chain length of vegetable oil) has also observed by
many research groups [67–72]. But, unburned hydrocarbon (UHC) has
always higher trend with any type of vegetable oil-based MHBF [48–50].
The CI engine emissions with respect to vegetable oil-based MHBF are
reviewed and mentioned.
CO emission is the result of incomplete combustion and it is recip­
rocal with an increase of load on the CI engine. Singh et al. [75] reported
that CO emissions for MHBFs showed a comparatively higher trend than
petrodiesel, but, Kumar and Singh et al. [71,75] results contradicted and
reported that CO emissions had lower trend than petrodiesel and almost
similar with B20 and B100. These differences have been clearly seen in
Fig. 10 which is in agreement with the variations in the composition of
MHBFs and chemical structures of vegetable oil feedstock.
It has been reported that the concentration of alcoholic components
in MHBF helps in CO reduction due to its higher rate of vaporization
[106–110]. CO emission was higher at low load conditions but, lower at
the part and full load condition [110–112]. This is attributed that at low
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Fig. 10. CO concentration for MHBFs w.r.t. load [27,71,75].

Fig. 11. CO2 concentration for MHBFs w.r.t. Load [71,75].

load condition, the in-cylinder temperature is also lower which partially
overcome the cooling effect created by alcohol but, at the same time at
medium and full load conditions, this can be easily overcome by
enhanced in-cylinder temperature and resulted in complete combustion
[113–116].
CO2 is the gaseous by-product during combustion in CI engine and its
concentration depends upon the combustion efficiency. However, MHBF
is a multi-component fuel system and the oxygenation characteristics of
MHBF depend upon the concentration of its components. As compared
to petrodiesel and biodiesel MHBF has a lesser carbon fraction and hence
less amount of CO2 generation on combustion as reported [117–120].
Fig. 11 also depicts that CO2 for MHBFs has lower than petrodiesel at full
load conditions [71]. However, various researchers reported that the
CO2 emission is directly proportional to the concentration of vegetable
oil in MHBF [121–125]. Due to the alcoholic content of MHBF, the
conversion of CO2 from CO was restricted attributed to faster evapora­
tion during combustion [126–128]. The same trend was observed by
Singh et. al [75] and it is evident from Fig. 11 that the higher concen­
tration of vegetable oil results higher CO2 emission.
NOx emission depends upon the in-cylinder temperature of the
combustible product, which is the result of fuel type, engine design, and
operating conditions as reported [129–131]. NOx emission for MHBFs
was reported to be lower than biodiesel and petrodiesel [71–75]. This is
the result of higher latent heat of vaporization of alcohol that reduces
the in-cylinder combustion temperature during combustion as compared
to that of biodiesel and petrodiesel [95–97]. The same trend was

11
H. Kumar et al.
Fig. 12. NOX concentration for MHBFs w.r.t. load [27,71,75].
Fig. 13. UHC concentration in MHBFs w.r.t. load [71].
reported by Kumar, Singh and Singh et al. [62,71,75], as depicted in
Fig. 12. A few research groups also reported that the use of water in
MHBF can reduce the formation of NOx. This could be due to the fact
that during combustion, water gets ionized, which lowers the formation
of OH radicals and drops down the formation of O atom resulting in the
reduction of formation of NO [81,82,132-134].
UHC emission form the CI engine depends upon the proper mixing of
air and fuel. However, the stoichiometric air-fuel ratio also shows that
the UHC emission is always higher for lean and rich air-fuel ratio
[60–62]. The UHC emission (Fig. 13) for MHBF was reported to be
higher than the petrodiesel [62,71,75]. This is due to the prolong
combustion duration, which accumulates more air-fuel mixture inside
the combustion chambers, hence a higher generation of UHC emission
due to incomplete combustion of charge. Also, this is in recounts to the
oxygenated nature of alcohol and the chemical structure of oil feedstock
that resulted in higher UHC emission and vice-versa [98–100]. Fig. 13
also depicts that UHC emission for JCO based MHBF is higher than WCO
based MHBF which is in agreement with the justification that more JCO
based MHBF was accumulated inside the cylinder to produce same
12
Renewable and Sustainable Energy Reviews 117 (2020) 109498
power which is the results of higher generation of UHC emission for JCO
based MHBF. There is a scope for future research to set injection timing
to assure complete burning and reducing UHC generation with MHBF.
The reason behind sulfur dioxide (SO2) emission from the CI engine
is the presence and concentration of sulfur in the injected fuel. Fig. 14
has depicted that the SO2 emission of MHBF shows a lower trend than
petrodiesel. The reason for low SO2 emission is due to very low sulfur
content in MHBF than petrodiesel as reported [75]. The concentration of
sulfur was reported to vary from oil to oil feedstock [75]. So, the gen­
eration of SO2 depends upon the percentage composition of vegetable
oil in MHBF.
Table 6 has presented the different emissions from CI Engine when
fuelled with MHBF with proper reasoning. Carbon monoxide (CO), un­
burned hydrocarbon (UHC), carbon dioxide (CO2), oxides of nitrogen
(NOx), sulfur dioxide (SO2) and smoke opacity have been taken into
consideration. Table 6 has also shown that different components of
MHBF demonstrated different emission profiles.
From the above discussion, it is pertinent to state that CI engine
emissions depend upon the combustion characteristics of MHBF. Many
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Table 6
Emission characterises of CI engine fuelled with various types of MHBF.
Emission Results Reasoning

Carbon Higher than petrodiesel at all The CO depends upon % of

monoxide engine load conditions [79]. ethanol in MHBF. The higher
(CO) Higher than biodiesel at low % of ethanol reduces CO
and medium load and almost emission due to the higher air-
identical at high engine load to-fuel ratio in MHBF.
[50,70,75,76]. The higher latent heat of
Higher at low and medium vaporization of ethanol creates
load but lower at high load cooling effect at part engine
than that of biodiesel (B100) loads, which results higher CO
and petrodiesel [77]. emission. At high load
Almost identical with B20, conditions due to high
B100 and petrodiesel at full temperature, ethanol burns
load condition [74]. effectively due to its short
Lower than petrodiesel [27] carbon chain and helps to
reduce CO emissions.
CO becomes higher at part
load conditions due to
Fig. 14. SO2 concentration for MHBFs w.r.t. load [75]. incomplete combustion but at
full load condition it becomes
lower due to increase
factors such as injection pressure, injection timing, air-fuel ratio, and volumetric efficiency because
fuel properties are responsible for complete combustion in the CI engine. of high oxygen content in
ethanol which leads to
For calibrated CI engine w.r.t. petrodiesel, MHBF has reported accept­
complete combustion.
able emissions [67,68,70–72]. Also, the key advantages with MHBF are This is due to high oxygen
very low NOx emission, low SO2 and very low smoke opacity as content in MHBF (45%
compared to petrodiesel. Further, a huge research scope is available alcohols) which improves its
with MHBF additives, including CI engine alteration and modification. atomization and combustion.
This is because of alcoholic
components in hybrid fuel
4. Microemulsion based hybrid fuels form non-renewable which results proper mixing
components during combustion.
Unburned Higher at low and part load This is because of higher latent
hydrocarbon but slightly lower at full load heat of evaporation of ethanol,
Table 7 shows the effects of different types of microemulsion based (UHC) than B100 [74]. which results low gas
fuel in CI engine. These types of blends are non-renewable in nature or Lower than B100 and temperature at low load. The
somehow prepared using non-renewable components. Petrodiesel was petrodiesel at high load same is somewhat overcome at
primarily used as a main component for this type of microemulsion condition [79]. full load condition.
Higher than B20, B100 and This is because of improved
blends and a commercial surfactant such as Span 20, Tween 20, Span 80
petrodiesel at all load evaporation and atomization
and Tween 80 were used to maintain their stability [Table 1]. In some conditions [67]. of MHBF which results proper
studies, biodiesel, ethanol, n-butanol any other alcohol was also used Higher than petrodiesel and mixing with air, hence
alone in combination but, at the same time non-renewable component all biodiesel blends [70]. complete combustion occurs at
was present in that fuel system. Table 7 has described about the per­ full load condition.
This is due to low volatility of
formance, combustion, and emission characteristics of CI engine fuelled vegetable oil as compared to
with different nonrenewable-based microemulsion blends. the other carbon fuels.
The reason behind higher UHC
5. Conclusion & future prospects is higher latent heat of
vaporization of alcoholic
components in hybrid fuel,
Among different types of biofuels, MHBF has been regaining which results heat absorption
importance as an economically viable and ‘green’ approach for liquid during combustion and
biofuel production from vegetable oils. MHBF is potentially a very good simultaneously reduce the in-
cylinder temperature, hence
aspirant to replace petroleum fuels and other biofuels for wider appli­
incomplete combustion
cations in CI engines. Nonetheless, further research is required to occurs.
improve the performance of the CI engine with MHBF formulation. Carbon dioxide Lower with high It depends upon concentration
Some major findings of this review are listed below: (CO2) concentration of ethanol and of ethanol in MHBF which
its reciprocal [75]. results lower CO2 with higher
Fairly lower than B20, B100 concentration of ethanol.
i. MHBF is the combination of 100% renewable components with and petrodiesel [79]. This is due to more oxygenated
no end products, consist of vegetable oil (lipid feedstock) (non- fuel which results lesser
polar), viscosity modifier (polar) and a surfactant or a combina­ amount of CO2 as engine
tion of surfactant and co-surfactant to form it stable. emission.
Oxides of Lower than petrodiesel [75]. This is because of aqueous
ii. A stable MHBF must have an optimum HLB value of surfactant,
nitrogen Slightly lower than B100 ethanol and butanol in MHBF
depending upon the type of emulsion (W/O type, O/W type), (NOx) [74]. which serves as a heat sink and
water concentration and amount of additive. Huge reduction in NOx than lowers the combustion
iii. A relatively low GCV of MHBF reduces BTE, BP, IMEP, and engine B100 and petrodiesel [92]. temperature and NOx
torque. The GCV of MHBF is also depended upon the chemical Five times lower than emission.
petrodiesel also lower than This is due to higher latent
structure of the oil feedstock and the exact composition of MHBF. B20 and B100 at all engine heat of evaporation of water
iv. Ignition delay is the main issue with MHBF based CI engine load conditions [71]. and ethanol which results a
during low and part load condition but, at high load condition (continued on next page)
MHBF shows appropriate ignition delay due to comparatively

13
H. Kumar et al. Renewable and Sustainable Energy Reviews 117 (2020) 109498

Table 6 (continued ) Table 7

Emission Results Reasoning
Other types of MHBF composition and its effect on CI engine.
Emulsion components Emulsion composition Effects on Engine
Lower than petrodiesel and decrement in local flame
performance, combustion
B100 for entire range of load temperature and therefore
and emission
conditions [97]. reduces the thermal NOx.
This is due to higher latent Vegetable oil-petrodiesel n.r. Carbon monoxide (CO)
heat of evaporation of water microemulsion with shows higher trend but
and alcohols in MHBF which surfactant & co-surfactant oxides of nitrogen (NOx)
results cooing during (W/O type) [29] shows lower than
combustion. petrodiesel.
This is because of lower Rapeseed oil-petrodiesel Petrodiesel 50–70% þ Combustion delay along
activation energy of MHBF blend with ethanol as a Rapeseed oil 20% þ with higher peak cylinder
than that of B20, B100 and surfactant and 1-butanol/ Ethanol 10–30% pressure (PCP), rate of
petrodiesel. oleic oil as a co-surfactant pressure rise (ROPR) and
This is because of higher latent [67] net heat release rate
of evaporation of ethanol and (NHRR) have been
1-butanol in hybrid fuel which observed in comparison
results low in-cylinder with petrodiesel.
temperature, hence low NOx Comparable BSFC with
emission. huge reduction in smoke
Smoke opacity Lower at high load than B100 This is because of lighter have also observed with
[75,79,81,82]. alcohol contents of MHBF with petrodiesel along with
Lower than that of B100 and low carbon/hydrogen ratio lower NOx at low engine
petrodiesel [27]. which results reduction in load condition.
Lower than petrodiesel and smoke. Petrodiesel- rapeseed oil Petrodiesel 70% þ Lower torque, BP and
biodiesel at part and full load This is due to microexplosion and n-butanol [80] rapeseed oil 20% þ EGT than B20, B100 and
engine condition [74]. in water and ethanol droplets 10% n-butanol petrodiesel. Also, higher
which results earlier BSFC, CO, NOx but
vaporization and turbulent reduced UHC have been
mixing of the fuel and air, observed.
hence reduction in soot Water (W) - rapeseed oil 80.5% FD þ 15% RO þ Higher BTE for RO
formation in the combustion (RO) - fossil diesel (FD), 2.5% W þ 2% (95.5%) and FD (95.5%)
chamber. water -fossil diesel, and surfactant (10% Tween based emulsion as
This is because of shorten C–H water - rapeseed oil with 80 þ 90% comparison with FD at
chain length, prolong ignition surfactant (Span 80 and Span 80). full load condition.
delay and prolong combustion Tween 80) [88] 78% FD þ 15% RO þ Comparable BSFC for
phase. 5% W þ 2% surfactant 80.5% FD þ 15% RO and
Sulfur dioxide Almost half with petrodiesel This is because of low sulfur (10% Tween 80 þ 90% FD (95.5%) based
[75]. content in MHBF. Span 80). emulsion at full load
95.5% ROþ 2.5% W þ condition.
2% surfactant (10% Higher CO2 for RO
high in-cylinder temperature which is facilitated by the micro­ Tween 80 þ 90% Span (95.5%) and FD (95.5%)
explosion in MHBF. 80). based emulsion as
95.5% FD þ 2.5% W þ comparison with FD at
v. In-cylinder pressure in CI engine shows higher or lower trend
2% surfactant (10% full load condition.
(depends upon the composition of MHBF) with petrodiesel and Tween 80 þ 90% Span Lower CO for FD (95.5%)
other biofuel blends. Different components of MHBF facilitate the 80). based emulsion at full
rate of microexplosion that plays a major role in the increase or load condition.
decrease of CI engine in-cylinder pressure. Lower NOx for RO
(95.5%), FD (95.5%),
vi. The emission profile with MHBF shows exponential reduction in 80.5% FD þ 15% RO and
NOx due to the higher latent heat of vaporization of alcohol which 78% FD þ 15% RO based
creates a cooling effect during combustion with a slight increase emulsion at all load
in UHC. In that respect it has immense scope for further research condition.
Identical O2 for 80.5% FD
with CI engine in terms of injection and ignition timing including
þ 15% RO based
variation in cylinder pressure to reduce the UHC emission, emulsion.
leading to complete combustion. Lower smoke opacity for
RO (95.5%), FD (95.5%),
From the extensive literature survey, it can be projected that MHBF 80.5% FD þ 15% RO and
78% FD þ 15% RO based
has the potential to replace petrodiesel and other alternative biofuels but emulsion.
a lot of work is still required to establish it as an effective fuel for CI Higher exhaust gas
engine application, particularly for heavy-duty vehicles and farm ma­ temperature for RO
chinery equipment. The effects of MHBF components such as alcohols (95.5%), FD (95.5%),
80.5% FD þ 15% RO and
(ethanol, n-butanol, etc.) and its effects upon long term operation od CI
78% FD þ 15% RO based
engine have also a matter of concern for future scope. Furthermore, emulsion at all load
there is a lot of scope for future research in areas such as additives for condition.
MHBF, cost analysis and optimization of CI engine input parameters. Tung oil- petrodiesel- Petrodiesel 30–50% þ Brake specific fuel
This work may remove the barrier for the commercialization of MHBF. ethanol and surfactant Tung oil 30% þ Ethanol consumption (BSFC) and
[92]. 20–40% brake thermal efficiency
This area of research is simple but may lead to revolutionary changes for (BTE) show slightly
bulk production of MHBF, new design and modification in CI engine if so higher trend than
required, for heavy-duty vehicles. The sustainability assessment of petrodiesel and Low
MHBF, exergy analysis and its long-term effects upon engine are also a smoke, NOx but slightly
higher unburned
matter of concern for future research work. Although long term storage
is not recommended for MHBF formulation, a simple method of (continued on next page)

14
H. Kumar et al.
Table 7 (continued )
Emulsion components Emulsion composition Effects on Engine
performance, combustion
and emission
hydrocarbon (UHC) and
CO emissions.
Diesel (D)- waste cooking 95% D þ 5% WBD Higher BP for 38, 75 and
oil biodiesel (WBD)- 95% D þ 5% WBDþ 38 150 μM based CNP as
water (W)- surfactant (S)- μM CNP compared to diesel at full
carbon nano particles 95% D þ 5% WBDþ 75 load condition.
(CNP) at different μM CNP Slightly lower BSFC for
concentrations, i.e., 38, 95% D þ 5% WBDþ 38 μM based CNP as
75, and 150 μM [109] 150 μM CNP (Each 01 compared to diesel at full
kg of 95% D þ 5% WBD load condition.
based blend contains Higher and comparable
75 mL emulsifier BTE for 38 and 150 μM
(polysorbate 80 and based CNP at full load
sorbitan monooleate condition as compared to
(1:2)) and water (30 g) diesel.
Higher UHC from diesel
for all emulsion blend at
full load condition than
microemulsion.
Higher UHC from diesel
for all emulsion blend at
full load condition.
Lower NOx for 38 and
75 μM based CNP in
comparison with diesel at
full load condition.
Lower CO2 from diesel for
all emulsion blend at full
load condition.
Higher O2 from diesel for
all emulsion blend at full
load condition.
Diesel (D)-water (W)- D with 2%, 5%, 8% and Lower BP and torque for
surfactant (S) [115] 10% by vol. of water all emulsion blends in
along with Span 80. comparison with diesel.
Higher BSFC except 2%
water emulsion in
comparison with diesel.
Highest BTE for 2% water
emulsion among other
emulsions and
petrodiesel.
Higher CO for all
emulsion in comparison
with diesel.
Lower CO2 except 2%
water emulsion in
comparison with diesel.
Higher BSFC except 5%
water emulsion in
comparison with diesel.
Lower NOx for all
emulsion blends in
comparison with diesel.
Jatropha biodiesel (JBD) JBD 85–95% þ WPO Higher BTE up to 7.4%
and Wood pyrolysis oil 5–15% þ Span 20 2% than petrodiesel. Lower
(WPO) [124] NOx but higher UHC than
B100 and petrodiesel.
preparation and stability for 3–6 months can easily motivate the
nontechnical personnel for its preparation and uses. The additional
recommendation includes a selection of suitable oil feedstocks with
known fatty acid composition for the preparation of MHBF is one of the
main areas of future research. A software-based technique for optimi­
zation of component’s proportion of MHBF has the potential for future
study. Use of bio-additives and carbon nanotubes (CNTs) to improve the
cetane number of MHBF, which can be explored to improve the per­
formance of CI engine and additives that can reduce the UHC. CI engine
input parameters such as fuel injection pressure, injection timing and air
intake pressure can be manipulated to enhance the performance of
existing CI engines with MHBF. As stated, earlier UHC emission was
15
Renewable and Sustainable Energy Reviews 117 (2020) 109498
found higher in every study and hence immediate exercise and excessive
attention are required to resolve this issue.
Acknowledgements
The author Himansh Kumar would like to thank MHRD, GOI for
teaching assistantship during PhD research work and SSS-NIBE Kapur­
thala, Punjab for platform of experimental works.
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