Applied Energy 178 (2016) 746–757

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Emulsification analysis of bio-oil and diesel under various combinations

of emulsifiers
Bo-Jhih Lin a, Wei-Hsin Chen a,⇑, Wojciech M. Budzianowski b, Cheng-Ting Hsieh c, Pei-Hsun Lin c
a
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
b
Wrocław University of Technology, 50-370 Wrocław, Poland
c
New Materials Research and Development Department, China Steel Corporation, Kaohsiung 812, Taiwan

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Emulsification characteristics of bio-

oils and diesel are studied.

The correlation of optimum HLB and
HHV provides the best result.

The developed correlations are
conducive to reducing operation cost.

The found mechanisms provide
practical insights into the preparation
of emulsions.

FTIR can precisely examine the
stability and homogeneity of
emulsified fuels.

a r t i c l e i n f o a b s t r a c t

Article history: Emulsification characteristics of bio-oils and diesel at various operating conditions are analyzed. Three
Received 15 March 2016 different commercial emulsifiers (i.e., Span 80, Tween 80, and Atlox 4914) and four bio-oils from fast
Received in revised form 17 June 2016 pyrolysis of wood wastes are studied. When the three emulsifiers are individually employed, the perfor-
Accepted 18 June 2016
mance of the emulsifiers is characterized by the order of Atlox 4914 > Span 80 > Tween 80. Atlox 4914,
Available online 29 June 2016
consisting of the hydrophilic portion of PEG and the hydrophobic portion of poly alkyd resin, has a better
performance. The HLB value of an emulsifier can be obtained by blending Span 80 and Tween 80 or Span
Keywords:
80 and Atlox 4914. The optimum HLB for the emulsification of bio-oils and diesel linearly increases with
Bioenergy
Pyrolysis and bio-oil
increasing the atomic O/C or H/C ratio, water content, and decreasing higher heating value (HHV) of bio-
Diesel oil. The correlation of the optimum HLB and HHV provides the best result, which can be employed for
Emulsification and emulsifier practical emulsification operation between bio-oils and diesel and is conduce to reducing operation cost.
Optimum HLB The functional groups in the emulsifiers, bio-oils, and diesel are analyzed by a Fourier transform infrared
FTIR spectra spectroscopy (FTIR) to recognize the characteristics of emulsions. It is found that FTIR is a fast and effec-
tive tool to examine the stability and homogeneity of emulsified fuels, even though no stratification is
observed. Accordingly, this developed method can be used to rapidly and precisely identify the perfor-
mance of emulsification in industry.
Ó 2016 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail addresses: weihsinchen@gmail.com, chenwh@mail.ncku.edu.tw (W.-H.
Chen).

http://dx.doi.org/10.1016/j.apenergy.2016.06.104
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.
 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757
1. Introduction
Pyrolysis is a crucial thermochemical process to convert bio-
mass into fuels and chemicals [1] where feedstocks are pyrolyzed
in a non-oxidative atmosphere at temperatures of 400–800 °C [2]
and bio-oils are main products. Bio-oils, if produced sustainably,
can be regarded as environment-friendly alternatives to fossil
fuels. This arises from the fact that they pertain to carbon–neutral
fuels and the net CO2 emission into the atmosphere is nearly zero
when they are burned. Moreover, most biomass contains only trace
amounts of sulfur and nitrogen [3], implying, in turn, that SOx and
NOx emissions from bio-oil combustion are negligible. In recent
years, a number of studies have successfully demonstrated the
burning of bio-oils in boilers, furnaces, Diesel engines, Stirling
engines, and gas turbines [1,4].
Bio-oils are sepia, opaque, and sticky liquids. The compositions
of bio-oils depend highly on feedstocks and operating conditions of
pyrolysis. Compared to fossil fuels, the oxygen concentration (44–
60 wt%), water content (15–30 wt%), viscosity (40–100 cP at 50 °C),
and acidity of bio-oils are high, whereas their higher heating value
(16–19 MJ kg1) is low and chemical and thermal stability is poor
[4–6]. For these reasons, bio-oils cannot directly replace high-
grade fuels such as gasoline or diesel, and need to be upgraded.
[7]. In this aspect, hydrotreating (e.g., hydrogenation and hydro-
deoxygeation), hydro-cracking, steam reforming, esterification,
emulsification, and chemical extraction have been developed to
improve bio-oil properties such as viscosity, calorific value, den-
sity, and water and oxygen contents [8].
Emulsification is a convenient, simple, inexpensive, and effec-
tive physical method to upgrade bio-oils for mixing diesel as a fuel
[9,10]. It has been reported that increasing bio-oils in diesel could
effectively reduce NOx emissions, but caused denser smoke in cer-
tain situations [11]. The addition of emulsifier (also called emulsi-
fying agent) into two immiscible streams (e.g., bio-oil and diesel)
with the help of agitation is an essential step to implement emul-
sification [12]. In an emulsion, the dispersed or droplet phase, also
termed internal phase, is encapsulated within a layer of the
continuous or external phase [3]. Nonionic surfactants are
excellent candidates to enter complex mixtures, and have been
Fig. 1. HLB values for different emulsions and mixture behaviors.
747
widely used as emulsifiers in that they are compatible with catio-
nic and anionic surfactants. In addition, they are much less sensi-
tive to electrolytes, particularly to divalent cations, than ionic
surfactants and can be used with high salinity or hard water. [13].
The hydrophilic–lipophilic balance (HLB) value, based on chem-
ical structure and surfactant properties, is an important parameter
for choosing emulsifier. Griffin [14] first established a HLB system
to classify nonionic surfactants. In the system, low HLB values are
ascribed to lipophilic surfactants, whereas hydrophilic surfactants
are featured by high HLB values. For a system using surfactants
with HLB values of 4–8, water-in-oil (W/O) emulsification is
obtained. Alternatively, oil-in-water (O/W) emulsification is exhib-
ited when surfactants with HLB values of 9–12 are employed [14–
18]. According to the above illustrations, the HLB values for differ-
ent emulsions and mixture behaviors are summarized in Fig. 1.
In recent years, some studies concerning the emulsification of
bio-oils and diesel have been reported. Chiaramonti et al. [15]
studied the production of emulsions from diesel and biomass fast
pyrolysis bio-oils for diesel engines. Ikura et al. [19] carried out a
series of emulsification experiments to determine the relationship
among process conditions, emulsion stability, and processing costs.
Jiang and Ellis [20] produced emulsions of bio-oils and biodiesel,
and investigated their stability affected by emulsifier concentra-
tion, bio-oil/biodiesel ratio, mixing temperature, and mixing time.
Lu et al. [21] prepared three different bio-oil/diesel emulsions at
different contents of bio-oils which were produced from rice husk
pyrolysis where the lubrication properties of emulsions, morpholo-
gies of emulsion surface, and chemical states of the elements on
worn and non-worn ball surfaces were analyzed. Martin et al.
[12] produced several emulsions, including bio-oil in diesel, and
examined their stability where an ultrasonic probe was used to
generate microscopic droplets of bio-oil suspended in diesel and
the emulsions were stabilized by means of surfactants. Prakash
et al. [22] investigated the combustion and emission characteris-
tics of emulsions made from wood pyrolysis oil and Jatropha
methyl ester, and compared with those of Jatropha methyl ester
and diesel operations. Yang et al. [11] pyrolyzed coffee bean
residue and tested emulsions of diesel and bio-oils in a single cylin-
der diesel engine connected to a 12-kW power generation system.
748 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757

Table 1
Literature review of emulsification.

Mixture Emulsifier HLB Objective Reference

Bio-oil, diesel, and Hypermer B246SF and Hypermer – A series of emulsification runs was carried out to determine the relationship [19]
emulsifier 2234 (mixed with MeOH) (5:2) between process conditions, emulsion stability, and processing costs
Bio-oil, diesel, and Octanol – Effects of several process variables such as emulsifier dosage, bio-oil/biodiesel [20]
emulsifier ratio, stirring intensity, emulsifying temperature, and mixing time on the
stability of emulsion over 24 h
Bio-oil, diesel, and Span 20, Span 80 and Span 100 – Bio-oil from the fast pyrolysis of biomass is a low-grade liquid fuel, which can be [21]
emulsifier upgraded through the emulsification with diesel oil
Bio-oil, diesel, and Span 85, Tween 85, Span 60, Brij 72, 4.25–5.75 Several emulsions consisting of biomass pyrolysis oil (bio-oil) in diesel fuel were [12]
emulsifier Zephrym PD 2206a, and Hypermer produced and analyzed for stability over time
B246
Bio-oil, biodiesel, Span 20 8.6 The use of bio-oil derived from the pyrolysis of wasted wood in a single cylinder, [22]
and emulsifier air cooled, direct injection (DI), diesel engine developing power of 4.4 kW at
1500 rpm used in agricultural and standby applications
Bio-oil, diesel, and Span-80, Tween-80 – A single cylinder diesel engine connected to a 12-kW power generation system [11]
emulsifier was used as the test system to examine the performance
Bio-oil, diesel, Span 80 with n-butanol, n-pentanol, – Effects of various emulsifying factors on bio-oil solubilization capacity, such as [17]
emulsifier, and n-hexanol, n-heptanol, and n- initial bio-oil/diesel volume ratio (B/D ratio), emulsifier concentration, and co-
co-emulsifier octanol emulsifier type, and the analysis of the properties of bio-oil/diesel emulsions
were carried out
Bio-oil, diesel, and Span-80, Tween-80, and Span-85 1.8–7.0 Emulsion fuels from crude bio-oil and its molecular distillation fractions were [23]
emulsifier prepared by single ultrasonic and ultrasonic-mechanical emulsification
Water and biodiesel – – A direct comparison of combustion and emission properties between gaseous [24]
fuel (dimethyl ether or DME), two emulsified fuels (5% and 10% water-in-RME
emulsions) and biodiesel (RME) are studied.
Water, diesel, Lignin – The use of water-continuous emulsions stabilized by a bio-based macromolecule [25]
biodiesel, and jet in a compression-ignition diesel engine and compare their performance,
fuel combustion and emissions against the base fuels (diesel, biodiesel, and jet fuel)
Water and biodiesel Span 80, PGO, Lecithin, Lanolin – Diesel-water emulsified fuel was produced and applied to a conventional diesel [26]
engine and to confirm the characteristic spray.
Water, diesel, and Span-80, Tween-80 9.6–10.4 Emulsions of water-in-diesel fuel mixed with nonionic surfactants were prepared [27]
emulsifier

Wang et al. [17] evaluated the solubilization capacity of bio-oil in the present study aims to explore the influence of the emulsifier’s
diesel under the influences of bio-oil/diesel volume ratio, surfac- HLB value on the performance of emulsification. A number of cor-
tant concentration, co-surfactant type (n-butanol, n-pentanol, n- relations based on bio-oil properties and optimum HLB value will
hexanol, n-heptanol, and n-octanol), and co-surfactant/surfactant be developed. Detailed emulsification mechanisms due to using
mass ratio. Guo et al. [23] prepared emulsions of diesel, crude different emulsifiers will be discussed. Moreover, Fourier trans-
bio-oil, and its molecular distillation fractions using single ultra- form infrared spectroscopy (FTIR) will be applied to examine the
sound and ultrasound-mechanical emulsification processes where homogeneity and stability of emulsions. The established correla-
the mechanisms of emulsification based on the composition and tions can provide a simple and fast method to estimate the optimal
fraction of the crude bio-oil were proposed to illustrate the varia- HLB for bio-oil and diesel emulsification, while the developed FTIR
tion of emulsion stability. technique is able to efficiently and precisely examine the homo-
In addition to emulsifying bio-oils and diesel, emulsification can geneity and stability of emulsions.
also be used to blend water and diesel or biodiesel. When the
emulsions of water and diesel are injected into a combustor,
2. Experimental
microexplosion may occur which facilitates combustion efficiency
and reduces NOx emissions [4]. Namasivayam et al. [24] produced
2.1. Bio-oils and emulsifiers
two emulsions of water and biodiesel, and compared their com-
bustion and emission characteristics to those of dimethyl ether
Bio-oils adopted in this study were produced from the fast
(DME) and biodiesel. Ogunkoya et al. [25] prepared high internal
pyrolysis of wood wastes. The pyrolysis was carried out in a flu-
phase ratio emulsions (70:30 fuel-to-water) by mechanical emulsi-
idized bed reactor at temperatures of 450–550 °C. Nitrogen was
fication using carboxymethylated wood lignin as emulsifier. Park
et al. [26] produced diesel-water emulsified fuels using four differ- Table 2
ent emulsifiers (Span 80, PGO, Lecithin, and Lanolin) for a diesel Properties of bio-oils.
engine, and evaluated the possibility of their applications to con- Bio-oil PB-1 PB-2 PB-3 PB-4
ventional diesel engines. A number of studies regarding the emul-
Physical appearance
sification of bio-oils or water in diesel using various emulsifiers are
summarized in Table 1 [11,12,19–27].
The literature reviewed above suggests that a number of studies
concerning the emulsification of bio-oils and diesel using a variety HHV (MJ kg1) 17.39 23.57 19.09 17.13
of emulsifiers such as Span 80, Tween 85, and Brji 72 [12,23] have (kcal kg1) 4154 5631 4561 4092
Density (g cm3) 1.17 1.36 1.22 1.02
been reported. When emulsions are produced from bio-oils and
Water content (wt%) 28.20 9.56 19.70 26.53
diesel, two important factors will influence the performance of pH 2.94 3.01 2.84 3.07
emulsification; they are the type and the HLB value of emulsifier
Elemental analysis (wt%)
[12,23]. However, relatively little research has been performed C 39.71 58.85 46.69 40.69
on the effect of HLB value upon a bio-oil/diesel emulsion system, H 9.05 7.12 6.92 7.41
especially in the relationship between bio-oil properties and emul- N 0.49 0.43 0.49 0.34
sifier’s HLB value for stabilizing emulsified fuels. For this reason, O (by difference) 49.85 33.60 46.40 51.56
 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757 749

Table 3 2.2. Experimental procedures

GC–MS of bio-oil PB-1.

Retention time (min) Area (%) Library ID 2.2.1. Emulsification test

In each emulsification run, 1g of emulsifier was loaded into a
23.47 1.15 Furfural
32.96 1.62 2(5H)-Furanone
centrifuge tube, followed by adding a certain amount of diesel fuel
35.26 5.96 1,2-Cyclopentanedione, 3-methyl- into the tube. A vortex mixer (CHIH CHIN H&W ENTERPRISE CO.,
35.92 6.56 Phenol, 2-methoxy- LTD, VM-2000) was employed to vibrate the tube for 1 min to
37.07 0.86 2-Cyclopenten-1-one, 3-ethyl-2 hydroxy- homogenize the solution of emulsifier and diesel fuel. Then, a cer-
38.44 6.93 Phenol, 2-methoxy-4-methyl-
tain amount of bio-oil was added into the tube, followed by mixing
39.53 6.19 Phenol
40.19 3.85 Phenol, 4-ethyl-2-methoxy- the emulsifier, diesel, and bio-oil by applying the vortex mixer for
41.27 1.72 Phenol, 2-ethyl- 2 min. Afterwards the tube was placed in a tube rack, and the phys-
41.94 1.06 Phenol, 2-methoxy-4-propyl ical appearance of the prepared emulsion was observed. If stratifi-
43.12 3.13 3-Allyl-6-methoxyphenol cation in the emulsion occurred, the length of the stratification
43.69 1.11 Phenol, 2,3,5,6-tetramethyl-
44.87 2.63 Phenol, 2-methoxy-4-(1-propenyl)-
layer in the emulsion with time was measured and recorded. Four
45.07 3.4 Phenol, 2,6-dimethoxy- diesel-to-emulsifier weight ratios (i.e., D/E ratios) of 10, 15, 20, and
46.56 7.53 Phenol, 2-methoxy-4-(1-propenyl)-(E)- 25, and seven bio-oil-to-emulsifier weight ratios (i.e., B/E ratios) of
47.62 2.65 4-Ethylbiphenyl 0.25, 0.5, 0.75, 1, 1.25, 2, and 2.25 were taken into account to test
49.04 0.95 5-Hydroxymethldihydrofuran-2-one
the emulsification behavior. To ascertain the experimental quality,
49.21 0.91 2-Furancarboxaldehyde, 5-(hydroxymethyl)-
49.83 1.09 Phenol, 2,6-dimethoxy-4-(2-propenyl)- some experiments were repeated twice and they showed high
50.33 2.28 Vanillin reproducibility and consistency.
51.54 2.03 Ethanone, 1-(4-hydroxy-3-methoxyphenyl)-
51.82 2.09 Homovanillyl alcohol
2.2.2. Optimum HLB
52.37 0.71 1,2-Benzenediol
52.82 1.77 Phenol, 2,6-dimethoxy-4-(2-propenyl)- To find the optimum HLB for bio-oil and diesel emulsification,
57.67 0.89 Benzeneactic acid, 4-hydroxy-3-mrthoxy- Span 80 (HLB = 4.3) was mixed with Tween 80 (HLB = 15) at differ-
69.85 14.82 3,4-Altrosan ent weight percentages to produce emulsifiers with HLB values of
4.3, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, and 8. The HLB value of an emulsifier
based on the weight percentages of Span 80 and Tween 80 can be
specified and calculated in accordance with the following equation
used as a carrier gas and the fluidization velocity in the reactor was [14]:
around 0.3 m s1. The designed capacity of the pyrolysis system
ðHLB1  W 1 þ HLB2  W 2 Þ
could feed biomass at a feeding rate of 30 kg-biomass h1 along HLB value of emulsfier ¼ ð1Þ
W 1 þ W2
with bio-oil production rate of 150 L d1. The produced vapors
from the reactor were cooled at around 50 °C to collect bio-oils. where W and subscripts 1 and 2 stand for weight percentage, emul-
The liquid yield from the pyrolysis was higher than 60 wt% and sifier 1, and emulsifier 2, respectively. In the procedure of determin-
up to 70 wt%. Four different pyrolysis bio-oils, termed PB-1, PB-2, ing the critical bio-oil content at a given HLB value, 20g of diesel and
PB-3, and PB-4, were tested. Their higher heating values (HHVs), 1g of emulsifier were loaded into a centrifuge tube and mixed by
densities, water contents, pH values, and elemental analyses are the vortex mixer. Then, 0.25g of bio-oil was dropped into the mix-
listed in Table 2. Table 3 shows the GC–MS analysis of PB-1, sug- ture, followed by mixing the mixture using the mixer for 2 min. If
gesting that the prime species in the bio-oil are phenols and phenol the emulsion was homogeneous after 10 min, 0.25g of bio-oil was
derivatives. Three different commercial emulsifiers (Croda Interna- added into the emulsion and mixed by the mixer again. This proce-
tional Plc), consisting of Span 80, Tween 80, and Atlox 4914, were dure was repeated until the stratification phenomenon was
used to perform the emulsification of io-oils and diesel. Span 80 observed. Accordingly, the critical bio-oil content at the specified
and Tween 80 have been used in some studies for bio-oils and die- HLB value was determined. The critical bio-oil contents at the
sel emulsification [11,15,17,21,23]. Atlox 4914 is the series of pro- HLB values of 4.3, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, and 8 were sequentially
duct from Croda Atlox series. The properties of the emulsifiers such tested. The HLB value with the highest critical bio-oil content was
as hydrophilic and lipophilic groups, HBL value, average molecular identified as the optimum HLB for the emulsification of bio-oil
weight, and density are shown in Table 4 [12,27–29]. and diesel.

Table 4
Properties of emulsifiers [12,27–29].

Emulsifier Span 80 Tween 80 Atlox 4914

Physical appearance

Chemical structure –

Hydrophilic group Sorbitan PEG* PEG

Lipophilic group Oleic acid Oleic acid Alkyd resin
HLB value 4.3 15 6
Molecular weight (g mol1) 429 1310 –
Density (g cm3) 0.99 1.08 0.97
*
PEG = polyethylene glycol.
750 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757

2.3. Bio-oil and emulsifier analysis
A number of analyses, composed of the calorific, elemental,
water content, and composition analyses, were performed to ana-
lyze the properties of bio-oils. The HHV of the bio-oils were mea-
sured by a bomb calorimeter (IKA C5000). The elemental analysis
was fulfilled using an elemental analyzer (PerkinElmer 2400 Series
II CHNS/O Elemental Analyzer) in which the weight percentages of
C, H, and N in bio-oils were measured. The weight percentage of O
in bio-oils was calculated by difference (i.e., O = 100-CAHAN). The
water content was measured by Karl Fischer titration (Metrohm
AG, 870 KF Titrino plus), following the procedure of ASTM
D1744. The compounds in bio-oils were detected by gas
chromatography (GC, Agilent 6890A with DB-WAX polar capillary
(a) Span 80
35

B/E=1.25
30
B/E=1
(a) Span 80 B/E=0.75
110
25

Stratification (mm)
B/E=0.5
B/E=0.25
100
20
3421 1457
Transmittance (%)

90
15
2847 1733
80 1175 712
2909 10
1062
70
5
60
0
5 10 15 20 25 30
50
D/E ratio
40
3500 3000 2500 2000 1500 1000 (b) Tween 80
Wavenumber (cm-1) 35

B/E=1.25
(b) Tween 80 30 B/E=1
110
B/E=0.75
25 B/E=0.5
Stratification (mm)

100
B/E=0.25
Transmittance (%)

90 3504 20
1732
2928 15
80 2860
1472 1348 840
70 10
941
60 5

50 0
1093
5 10 15 20 25 30
40 D/E ratio
3500 3000 2500 2000 1500 1000
Wavenumber (cm-1) (c) Atlox 4914
30
(c) Atlox 4914
110
25
100 B/E=2.25
3501
Stratification (mm)

20 B/E=2
Transmittance (%)

90 B/E=1.25
1740 B/E=1
80 2936 2848 15 B/E=0.5
1458 848
950
70 1368
1102 10

60
5
50

0
40 5 10 15 20 25 30
3500 3000 2500 2000 1500 1000 D/E ratio
-1
Wavenumber (cm )
Fig. 3. Profiles of stratification layer in emulsified fuels using the emulsifiers of (a)
Fig. 2. FTIR spectra of (a) Span 80, (b) Tween 80, and (c) Atlox 4914. Span 80, (b) Tween 80, and (c) Atlox 4914.
 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757 751

(a) PB-1 (17.39 MJ kg )

-1
(b) PB-2 (23.57 MJ kg -1)
1.5 1.5

1.25 1.25

Bio-oil content (g)

Bio-oil content (g)

1 1

0.75 0.75

0.5 0.5

0.25 0.25

0 0
4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5
HLB value HLB value

-1 -1
(c) PB-3 (19.09 MJ kg ) (d) PB-4 (17.13 MJ kg )
1.5 1.5

1.25 1.25
Bio-oil content (g)
Bio-oil content (g)

1 1

0.75 0.75

0.5 0.5

0.25 0.25

0 0
4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5
HLB value HLB value

Fig. 4. Distributions of critical bio-oil content in emulsions using bio-oils of (a) PB-1, (b) PB-2, (c) PB-3, and (d) PB-4. (D/E = 20).

column) in association with a mass spectrometer (MS, Agilent
5973 N). The GC oven temperature was (1) kept at 40 °C for
5 min, (2) increased to 110 °C at a heating rate of 5 °C min1, (3)
increased to 150 °C at a heating rate of 3 °C min1, (4) increased
to 250 °C at a heating rate of 5 °C min1, and then (5) kept at
250 °C for 20 min. That is, the analysis time of bio-oils in the GC
was around 70 min. The functional groups in the emulsifiers and
bio-oils were analyzed through a Fourier transform infrared spec-
troscopy (FTIR, PerkinElmer/Spectrum 100). The adopted instru-
ments were calibrated periodically to guarantee the analysis
quality.
3. Results and discussion
3.1. FTIR spectra of emulsifiers
Three commercial nonionic surfactants of Span 80, Tween 80,
and Atlox 4914 are adopted to examine the emulsification of bio-
oil PB-1 in diesel. The main hydrophilic groups in these emulsifiers
are sorbitan and polyethylene glycol (PEG), which contain many
polar groups, and the main lipophilic groups are fatty acids, fatty
alcohols, and esters, which contain long and nonpolar hydrocarbon
chains. The FTIR spectra of the three emulsifiers are shown in Fig. 2
to examine their functional groups. The characteristic peaks at
3421, 3504, and 3501 cm1 are due to OAH stretching vibration
in the three emulsifiers [30,31]. The peaks at 2845–2870 cm1
and 2915–2949 cm1, as a result of aliphatic CAH stretching vibra-
tion, are also observed in these emulsifiers [30,32]. Unlike Tween
80 and Atlox 4914 where the aforementioned two peaks merge
together, the two peaks in Span 80 are individually exhibited
(Fig. 2a), likely due to the structure with less branches in Span
80. The peaks at 1732–1740 cm1 are due to C@O structure
stretching vibration of ester groups in the three emulsifiers [30].
The peaks at 1446–1486 cm1 and 1371–1382 cm1 are attributed
to CAH bending symmetric, asymmetric, or scissoring vibration
[33]. However, the second peak is not exhibited in Span 80. The
peaks at 1175, 1102, 1093, and 1062 cm1 are the consequence
of CAOAC stretching vibration of ester [30,34]. Peaks at
1093 cm1 in Tween 80 (Fig. 2b) and at 1102 cm1 in Atlox 4914
(Fig. 2c) are clearly identified. In contrast, the peaks at 1175 and
1062 cm1 in Span 80 (Fig. 2a) are not as significant as those in
Tween 80 and Span 80, implying that there is a pronounced dis-
crepancy in the CAOAC structure of ester. The peaks at 712–
950 cm1 is owing to CAH deformation vibration which can be
found in the three emulsifiers [35,36].
3.2. Emulsification characteristics
Emulsions are normally categorized into two different types:
one is dispersion of water droplets in oil (W/O emulsion), and
the other is oil droplets in water (O/W emulsion) [15]. Despite
the bio-oil being referred to as ‘‘oil”, it contains water and other
752 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757

(a) O/C ratio (b) H/C ratio

9 9
8.5 8.5
8 y=2.2762x + 3.8181 8
R 2=0.9225
7.5 7.5 y=0.7550x + 3.9588
Optimum HLB

Optimum HLB
2
7 7 R =0.7482
6.5 This study 6.5
6 6
5.5 5.5
5 Martin et al. [12] 5
4.5 4.5
4 4
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
O/C ratio H/C ratio

(c) Water content (d) Higher heating value

9 9
8.5 8.5
8 y= 0.0558x + 4.3742 8
y=-0.1856x + 9.1813
7.5 R 2=0.9377 7.5
Optimum HLB

R 2=0.9724
Optimum HLB

7 7
6.5 6.5
6 6
Hsieh et al. [37]
5.5 5.5
5 5
4.5 4.5
4 4
0 20 40 60 80 5 10 15 20 25 30
Water content (wt%) Higher heating value (MJ/kg)

Fig. 5. Profiles and linear regressions of optimum HLB versus (a) atomic O/C ratio, (b) atomic H/C ratio, (c) water content, and (d) higher heating value in bio-oils.

polar liquids. It should be addressed that, in an emulsification sys-
tem of bio-oil in diesel, the bio-oil actually forms the ‘‘water” phase
in the emulsion, while diesel fuel, which is composed of nonpolar
hydrocarbons, forms the true ‘‘oil” phase [12].
The stratification distributions of emulsions at various B/E and
D/E ratios are shown in Fig. 3 where PB-1 was used and the mea-
surements were carried out after 24 h of the onset of emulsifica-
tion. Overall, the emulsification performance is characterized by
the order of Atlox 4914 > Span 80 > Tween 80. Meanwhile, the
higher the B/E ratio, the more pronounced the bio-oil deposition,
irrespective of emulsifier. This can be explained by more difficult
emulsification for the addition of more bio-oil into diesel. When
Span 80 and Tween 80 were used, the stratification layers were
in the ranges of 4.5–10 mm (Fig. 3a) and 13–20 mm (Fig. 3b),
respectively. While mixing PB-1, diesel and an emulsifier, the
hydrophilic groups in the emulsifier catch bio-oil particles. The
hydrophilic groups of polyethylene glycol (PEG) in Tween 80 are
larger than those of sorbitan in Span 80. The interaction between
larger hydrophilic groups in Tween 80 and PB-1 is stronger, making
cluster formation and thereby more obvious deposition. In con-
trast, the stratification layer using Atlox 4914, ranging from
0 mm to 1 mm (Fig. 3c), is by far smaller when compared to those
using Span 80 and Tween 80. The study of Martin et al. [12] found
that the emulsifier of polyethylene glycol dipolyhydroxystearate
(PEG–DPHS) used in the emulsification of pyrolysis bio-oils in die-
sel had high performance. In addition, emulsifiers with HLB values
close to 6 (e.g. Atlox 4912, Hypermer B246) for the mixing of
bio-oil and diesel were found to have better performance of emul-
sification [15,19]. In this study, Atlox 4914 with HLB value of 6,
having the hydrophilic portion of PEG and the hydrophobic portion
of poly alkyd resin (Table 4) [29], also has better performance for
the emulsification of the bio-oil in diesel. From the observed
results, it is concluded that using Atlox 4914 as a surfactant is more
appropriate than Span 80 or Tween 80 for practicing the emulsifi-
cation of bio-oils and diesel and the applications of bio-oils in
industry.
3.3. Correlations of optimum HLB for emulsification
A critical bio-oil content may exist for the emulsification of bio-
oil and diesel when an emulsifier is used; that is, the emulsion is
homogenous when the bio-oil content is smaller than or equal to
the critical one. The profiles of critical bio-oil content for the emul-
sification of the four bio-oils (i.e., PB-1, PB-2, PB-3, and PB-4) at
various HLB values are displayed in Fig. 4 where the D/E ratio
and diesel are fixed at 20 and 20 g, respectively. The profiles depict
that the critical bio-oil content is between 0.25 g and 1.25 g,
depending obviously on the HLB value. Corresponding to PB-1,
PB-2, PB-3, and PB-4, the optimum HLB values are 6.0, 5.0, 5.5,
and 6.0, respectively. These results reveal that the HLB values of
bio-oils should be controlled at around 5.0–6.0 for their practical
applications in diesel engines or boilers.
The profiles of atomic O/C and H/C ratios, water content, and
HHV of bio-oil versus optimum HLB are plotted in Fig. 5. The
 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757 753

Table 5
(a) Bio-oil (PB-1)
Weight percentages of emulsifiers at the optimum HLB values for bio-oil 100
emulsification.

Bio- HHV Optimum Emulsifier Emulsifier

oil (MJ kg1) HLB 1512
Span 80 Tween 80 Span 80 Atlox 4914
90
(wt%) (wt%) (wt%) (wt%)
PB-1 17.39 5.94 84.67 15.33 3.53 96.47

Transmittance (%)
PB-2 23.57 4.76 95.70 4.30 72.94 27.06 2924
PB-3 19.09 5.62 87.66 12.34 22.35 77.65 80
PB-4 17.13 5.99 84.21 15.79 0.59 99.41
1262
3386
1631
results of Martin et al. [12] and Hsieh et al. [37] are also included in 70 1705 1086
the figure. Fig. 5a–c depicts that a bio-oil with higher O/C ratio, H/C 1031
ratio, water content, or lower HHV has a larger optimum HLB
value. This arises from the fact that bio-oils with higher O/C ratios 60
and water contents possess stronger polarity and hydrophilicity,
and hydrophilic emulsifiers have high HLB values, as described ear-
lier. It has been reported that more water in a bio-oil decreased its
50
3500 3000 2500 2000 1500 1000
(a) Span 80 & Tween 80 -1
25 Wavenumber (cm )

(b) Diesel
PB-1 100
20 PB-2
PB-3
PB-4 90
Stratification (mm)

1373 722
15
Transmittance (%)

1452

80
10

2856
70
5
2920

60
0
0 5 10 15 20 25 30 35 40
Time (day)
50
3500 3000 2500 2000 1500 1000
(b) Span 80 & Atlox 4914 Wavenumber (cm-1)
25

Fig. 7. FTIR spectra of (a) bio-oil PB-1 and (b) diesel.

20
HHV [38,39]. This implies, in turn, that a bio-oil with lower water
content has lower polarity. This is the reason why an increase in
HHV tends to lessen the optimum HLB value, as shown in Fig. 5d.
Stratification (mm)

15 Table 6
Main functional groups of emulsifiers and bio-oils in FTIR spectra.

Wave number range (cm1) Functional group Mode of vibration Reference

10 3450–3550 Dimeric OAH Stretching [35]

3230–3400 Polymetric OAH Stretching [35]
2915–2949 Aliphatic CAH Stretching [34,35]
2858–2924 Aliphatic CAH Stretching [30]
5 1732–1740 C = O (ester) Stretching [30]
1640–1651 C = C (aromatic) Skeletal [33]
1579–1652 CAC (ring) Stretching [36]
1446–1486 CAHA(CH3) Symmetric [33]
CAHA(CH2) Asymmetric
0
1371–1382 CAHA(CH3) Symmetric [33]
0 5 10 15 20 25 30 35 40
1140–1230 CAO (phenol) Stretching [35]
Time (day) 1100–1239 CAOAC (ester) Stretching [31,34]
1070–1150 CAOAC (ester) Stretching [30]
Fig. 6. Distribution of stratification layer in emulsions with the emulsifiers of (a) 1049–1090 CAO Stretching [36]
Span 80 and Tween 80 blend and (b) Span 80 and Atlox 4914 blend for 40 days. (B/ 1006–1043 CAO Stretching [33]
E = 1 and D/E = 20).
754 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757

(a) Span 80 & Tween 80 (b) Span 80 & Atlox 4914

110 110
Top Top
100 100
Transmittance (%)

Transmittance (%)
90 90

80 1 day 80
40 day
70 70

60 60

50 50
3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1) Wavenumber (cm-1)

110 110
Middle Middle
100 100

Transmittance (%)
Transmittance (%)

90 90

80 80

70 70

60 60

50 50
3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1) Wavenumber (cm-1)

110 110
Bottom Bottom
100 100
Transmittance(%)

Transmittance (%)

90 90

80 80

70 70

60 60

50 50
3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm ) Wavenumber (cm-1)

Fig. 8. FTIR spectra of bio-oil PB-1/diesel emulsion with (a) Span 80 & Tween 80 (b) Span 80 & Atlox 4914for 1 and 40 days. (B/E = 1 and D/E = 20).

The linear regressions of the four physical quantities (i.e.,
atomic O/C and H/C ratios, water content, and HHV of bio-oil) with
respect to the optimum HLB value and their coefficients of deter-
mination (i.e., R2) are also provided in Fig. 5. As a whole, the regres-
sion lines are correlated well in that the smallest R2 is 0.7482. A
comparison among Fig. 5a–d indicates that the correlation of
HHV and optimum HLB yields the best liner relationship where
R2 is 0.9724. The study of Hsieh et al. [37] also obtained the linear
behavior between HHV and optimum HLB. Martin et al. [12] exam-
ined the emulsification of diesel and bio-oil with the HHV of
23.5 MJ kg1. According to their emulsification, the predicted opti-
mum HLB based on the correlation given in Fig. 5d is 4.78 which is
close to their experimental result of 4.75. The relative error
between the experiment and prediction is 0.63%. This reveals that
the correlation can be used to rapidly determine the optimum HLB
for emulsifying bio-oils and diesel, thereby saving much time to
find the optimum HLB value for the emulsification. Furthermore,
the operating cost of emulsification due to using less emulsifier
can be lowered.
3.4. Performance of emulsification under optimum HLB value
The correlation given in Fig. 5d can be rearranged as
Optimum HLB ¼ 0:1856  HHV þ 9:1813 ð2Þ
Based on this equation, the optimum HLB values for the emul-
sifications of PB-1, PB-2, PB-3, and PB-4 are 5.94, 4.76, 5.62, and
5.99, respectively. These values can be obtained by blending Span
 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757
20
Span 80 & Tween 80
15 Span 80 & Atlox 4914
Stratification (mm)
10
5 presence of alkyl CAH[32]. The peak at 1705 cm1 is attributed
0 skeletal vibration and stretching of C@C in aromatic rings, respec-
0 5 10 15 20 25 30 35 40
Time (day)
Fig. 9. Distribution of stratification in bio-oil/ diesel emulsion with different
emulsifiers under for 40 days. (B/E = 2 and D/E = 20).
80 and Tween 80 or Span 80 and Atlox 4914, whereas the mixtures
of Tween 80 and Atlox 4914 cannot attain the desired optimum
HLB values. The concentrations (wt%) of the emulsifiers for the
optimum HLB values are shown in Table 5. The emulsions at B/
E = 1 and D/E = 20 at the optimum HLB values were observed for
40 days to examine the performances of blended emulsifiers, and
the stratification distributions are shown in Fig. 6. Overall, the
emulsification performance from Span 80 and Atlox 4914 blends
(Fig. 6b) is by far better than that from Span 80 and Tween 80
blends (Fig. 6a). Accordingly, it should be pointed out that the
emulsification performance is sensitive to the emulsifier blends,
even though they have the same optimum HLB value. Meanwhile,
once the stratification develops on the first day, it appears to
become steady. This reflects that, after the onset of emulsification,
one- or 3-day observation may be sufficiently long for the stability
test.
In Span 80 and Tween 80 blends, Tween 80 has stronger inter-
action with the bio-oils. This is the reason that a higher Tween 80
content in Table 5 has a trend to increase the stratification layer in
Fig. 6a. In Fig 6b, no stratification was observed when mixing PB-1
or PB-4 with the blends of Span 80 and Atlox 4914. However, the
stratification is exhibited in PB-2 and PB-3, and the stratification
layer in PB-2 (=7 mm) is higher than that in PB-3 (=2 mm). That
may be due to the density difference between the bio-oils and die-
sel in the emulsions. Perazzo et al. [40] reported that stratification
tended to occur at high density differences between bio-oil and
diesel, stemming from the increase in the relative velocity between
the dispersed phase (bio-oil) and the continuous phase (diesel).
The densities of PB-2, PB-3, and diesel are 1.36, 1.22, and
0.81 g cm3, respectively. On account of higher density of PB-2, this
results in the higher stratification layer in the emulsion of PB-2,
diesel, Span 80, and Atlox 4914. In summary, the interaction
between bio-oil and Tween 80 with a high HLB value (=15) plays
an important role in determining the emulsification performance
when the blends of Span 80 and Tween 80 are used as emulsifiers.
Alternatively, the density difference between bio-oil and diesel
corresponds to the emulsification performance when the blends
of Span 80 and Atlox 4914 are adopted. These findings in emulsifi-
cation mechanisms are conducive to the practical operation and
recognition of bio-oil and diesel emulsification.
755
3.5. FTIR analysis
A number of methods can be utilized to evaluate emulsion sta-
bility such as measuring the pH value, viscosity, water content, or
droplet size distribution in an emulsion, and observing stratifica-
tion [19,41,42]. However, there is no standard procedure for exam-
ining the long term stability yet [42]. In the present study, FTIR is
used as a tool to examine the long term stability of emulsified
fuels.
The FTIR spectra of PB-1 and diesel are shown in Fig. 7. For PB-
1, the characteristic peak at 3386 cm1 shown in Fig. 7a is due to
OAH stretching vibration, and the peaks between 3000 cm1 and
2840 cm1 represent CAH stretching vibration, indicating the
to C@O stretching vibration of carbonyl groups, revealing the pres-
ence of ketones, aldehydes, and carboxylic acids in the bio-oil
[32,43]. The peaks at 1631 cm1 and 1512 cm1 stand for the
tively [33]. The peaks between 1280 cm1 and 1000 cm1 corre-
spond to CAO vibration, suggesting the possible presence of
acids, phenols, or alcohols in the bio-oil [32]. The employed com-
mercial diesel is a mixture made up of C9–C18 hydrocarbons. The
characteristic peaks at 2920 cm1 and 2856 cm1 in Fig. 7b are
due to aliphatic CAH stretching vibration. The peaks at 1452 and
1373 cm1 stem from CAH symmetric, asymmetric, or scissoring
bending [33]. The peak at 722 cm1 is a consequence of CAH
deformation vibration [35,36]. The main functional groups of
emulsifiers and bio-oils in the FTIR spectra are summarized in
Table 6.
In Fig. 6a and b, no stratification in the emulsions was observed
when PB-1 was used. To ascertain this conclusion, the two emul-
sions were analyzed using FTIR where the emulsified fuels at top,
middle, and bottom zones in the tube after 1 and 40 days were
sampled. The FTIR spectra shown in Fig. 8 depict that the curves
at the three zones are identical. Moreover, the spectra at the two
different durations overlap each other. This clearly indicates the
homogeneity and stability of the emulsions.
To figure out the effect of B/E ratio on emulsification, PB-1
emulsified by Span 80 and Tween 80 blend as well as Span 80
and Atlox 4914 blend at B/E = 2, D/E = 20, and HLB = 5.94 are
examined. Fig. 9 depicts that no stratification is exhibited when
the second blend is employed. However, the stratification appears
when the first blend is used and the stratification layer is 12 mm
which is steady for the duration between 1 and 40 days. The FTIR
spectra of the two emulsified fuels are displayed in Fig 10. For the
emulsion using the first blend (Fig. 10a), the spectra at the top
and middle zones almost overlap together which resemble that
of diesel (Fig. 7b). It is of interest that that the spectrum at the
bottom zone of the emulsion for 1 day is different from that for
40 days. Considering the emulsion for 1 day, the spectrum is
simultaneously characterized by PB-1 and diesel. As for the emul-
sion for 40 days, the spectrum approaches that of PB-1 (Fig. 7a).
This elucidates the variation in the nature of stratification layer.
When the second blend is used, the spectra of the emulsified fuel
for 1 day at the three zones are almost identical (Fig 10b) and
resemble that of diesel, revealing the homogeneity of the emul-
sion. For the emulsified fuel for 40 days, however, the spectrum
at the bottom zone is different from those at the top and middle
zones, and the peaks of bio-oil at 1237 and 1031 cm1 are found.
Accordingly, it should be addressed that the emulsion for 40 days
is not homogenous any more, even though no stratification is
observed. It is thus concluded that the conducted method using
FTIR is an easy and powerful tool to examine the homogeneity
and stability of prepared emulsions.
756 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757

(a) Span 80 & Tween 80 (b) Span 80 & Atlox 4914

110 110
Top Top
100 100

Transmittance (%)
Transmittance (%)

90 90

80 1 day 80
40 day
70 70

60 60

50 50
3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

110 110
Middle Middle
100 100

Transmittance(%)
Transmittance (%)

90 90

80 80

70 70

60 60

50 50
3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

110 110
Bottom Bottom
100 100
Transmittance(%)

Transmittance(%)

90 90

80 80

70 70

60 60

50 50
3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 10. FTIR spectra of bio-oil (PB-01)/diesel emulsion with (a) Span 80 & Tween 80 (b) Span 80 & Atlox 4914 under B/E = 2 and D/E = 20 for 40 days.

4. Conclusions
Emulsification stability and stratification characteristics of bio-
oils and diesel under the influences of types of emulsifier, HLB
value, and bio-oil/emulsifier (B/E) and diesel/emulsifier (D/E) ratios
have been investigated experimentally where three commercial
emulsifiers (i.e., Span 80, Tween 80, and Atlox 4914) and four
bio-oils (i.e., PB-1, PB-2, PB-3, and PB-4) from the fast pyrolysis
of wood wastes were employed. The results suggest that Atlox
4914 provides the best performance compared to Span 80 and
Tween 80 inasmuch as its hydrophilic portion of polyethylene gly-
col (PEG) and hydrophobic portion of poly alkyd resin can homog-
enize the solution of bio-oil and diesel. The correlations of
optimum HLB with respect to the atomic O/C and H/C ratios, water
content, and higher heating value (HHV) of bio-oils are strongly
characterized by linear distribution, and the last correlation yields
the best result (R2 = 0.9724). Accordingly, an easy way of finding
optimal HLB value for producing feasible emulsifier and high-
performance emulsification has been developed. This conducted
correlation can also accomplish the goal of lowering the costs of
emulsifier and the emulsification of bio-oils and diesel. When the
mixtures of Span 80 and Tween 80 are used, the emulsification per-
formance can be explained from the interaction of bio-oil and
Tween 80. Alternatively, the density difference between bio-oil
and diesel corresponds to the performance when the blends of
Span 80 and Atlox 4914 are utilized. These mechanisms have pro-
vided practical insights into the preparation of emulsions from
emulsifiers, bio-oils, and diesel. Detailed functional groups in the
 B.-J. Lin et al. / Applied Energy 178 (2016) 746–757
emulsifiers, bio-oils, and diesel can be figured out from FTIR anal-
ysis. In some tests, stratification in emulsions was not observed.
However, the FTIR analysis indicated that the homogeneity of the
emulsions had essentially changed. It is thus addressed that the
developed method using FTIR is a simple, fast, effective, and pre-
cise tool to examine the homogeneity and stability of emulsions.
It should be illustrated that the obtained results and developed
methods are conducive to implementing emulsification of bio-oil
and diesel in industry, thereby extending the applications of bio-
oils from biomass pyrolysis.
Acknowledgments
The authors gratefully acknowledge the financial supported
from the Ministry of Science and Technology, Taiwan, ROC, and
bio-oils supplied from the China Steel Corporation for this study.
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