Applied Energy 163 (2016) 7180

Contents lists available at ScienceDirect

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

Investigation of particulate emission characteristics of a diesel engine

fueled with higher alcohols/biodiesel blends
Zhi-Hui Zhang, Rajasekhar Balasubramanian
Department of Civil and Environmental Engineering, Faculty of Engineering, National University of Singapore, 1 Engineering Drive 2, E1A 02-19, Singapore 117576, Singapore

h i g h l i g h t s
 Blending butanol or pentanol with biodiesel changed the DPM characteristics.
 The blends reduced EC and DPM emissions, but increased WSOC and OC fractions.
 They reduced emissions of total particle-phase PAHs and also carcinogenic potential.
 They showed different effects on counts of nanoparticles and lager particles.

a r t i c l e

i n f o

Article history:
Received 4 May 2015
Received in revised form 25 October 2015
Accepted 30 October 2015
Available online 18 November 2015
Keywords:
Diesel engine
Biodiesel
Higher alcohols
Particulate emissions
PAHs

a b s t r a c t
A systematic study was conducted to make a comparative evaluation of the effects of blending n-butanol
and n-pentanol with biodiesel at 10% and 20% by volume on engine performance and on the physicochemical characteristics of particulate emissions from a single cylinder, direct injection diesel engine.
The engine was operated at a constant engine speed and at three engine loads. Compared to biodiesel,
butanolbiodiesel blends lead to a maximum of 1.6% increase in the brake thermal efficiency (BTE)
and an increase in the brake specific fuel consumption (BSFC) by 1.93.9% at low and medium engine
loads. Pentanolbiodiesel blends result in an improvement in the BTE and a maximum of 2% increase
in the BSFC. Compared to biodiesel, both the blended fuels can reduce the particulate mass and elemental
carbon (EC) emissions, with butanol being more effective than pentanol. The blended fuels also show a
lower emission of total particle-phase polycyclic aromatic hydrocarbons (PAHs) and also a lower carcinogenic potential. However, the proportion of particulate-bound organic carbon (OC) and water-soluble
organic carbon (WSOC) are increased for the both blended fuels, especially for 20% butanol in blends.
The emissions of volatile and solid particles are reduced significantly in terms of their counts for both
kinds of blended fuels at medium and high engine loads, whereas the total particle counts for both
10% and 20% butanol in blended fuels are increased at low engine load due to a significant increase in
particles with diameter less than 15 nm.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Research on the use of sustainable and cleaner fuels in internal
combustion (IC) engines for both mobile and stationary applications continues to receive considerable attention because of the
motivation to reduce our dependence on conventional fossil fuels
and to mitigate environmental and health impacts [1]. Among
the proposed alternative fuels, biodiesel and alcohols are the most
widely investigated ones in diesel engines for reducing diesel fuel
consumption and toxic emissions [24]. Biodiesel is renewable,
nontoxic and readily biodegradable, has no aromatic compounds,
Corresponding author. Tel.: +65 65165135; fax: +65 67744202.
E-mail address: ceerbala@nus.edu.sg (R. Balasubramanian).
http://dx.doi.org/10.1016/j.apenergy.2015.10.173
0306-2619/ 2015 Elsevier Ltd. All rights reserved.

and possesses a high cetane number, high flash point and also
excellent lubricity performance [57]. It has been widely reported
that substantial reduction in hydrocarbon (HC), carbon monoxide
(CO) and diesel particulate matter (DPM) emissions can be
achieved through the application of biodiesel from various feedstocks in diesel engines [26]. Despite its many advantages, the
direct application of pure biodiesel, or the use of high percentage
of biodiesel in diesel blends may cause a poor atomization and
incomplete combustion, carbon deposits or clogging of fuel lines,
as well as thickening and gelling of the engine lubricating oil due
to its poor volatility and high viscosity [6,810]. These major drawbacks of biodiesel limit its proportion in diesel blends, typically
about 20% [10]. Apart from biodiesel, lower alcohols, mainly
methanol and ethanol, in combination with diesel fuel, have been

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Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

widely investigated for reducing the NOx and the particulate emissions [3,4]. However, some practical difficulties prevent their use
as fuels in diesel engines, such as reduced lower heating value
(LHV) compared to diesel fuel, miscibility and stability problems
when blended with diesel fuel, low cetane number, high autoignition temperature and poor lubricating properties [810].
Although several approaches have been attempted to resolve or
alleviate the problems, there are still some challenges when applying these lower alcohols into practical applications. For example,
on the one hand, immiscibility can be overcome by using emulsifiers to form a micro-emulsion with methanol or ethanol [9,10],
or by directly injecting them into the air intake [11]; both of these
alcohols could be combined with the preheating of intake air to
improve ignition and vaporization [9,10]. However, these processes require either skilled technical expertise, or complex engine
hardware modifications making these options unattractive for
practical applications. On the other hand, blending diesel with
methanol or ethanol with certain stabilization additives and cetane
enhancers seems to be preferred because of its simplicity with no
need to modify the existing engine. However, the percentage of
alcohols in diesel blends is usually restricted to 510%, and additives could be costly [9]. The use of higher alcohols such as butanol
and pentanol blended with diesel fuel in diesel engines has
recently drawn considerable research attention due to higher miscibility with diesel [1217]. However, the fuel properties such as
lubricity, viscosity, and cetane number of higher alcoholsdiesel
blends still need to be improved [12].
Blending of biodiesel with both lower and higher alcohols can
simultaneously overcome the above-mentioned disadvantages of
biodiesel and alcohols and has therefore been extended to their
application in diesel engines [5,710,1821]. For example, biodiesel and alcohols are miscible to some extent without any need
for an emulsifier or a co-solvent. In the blended fuels, the lower
viscosity and higher volatility of alcohols compensates for these
opposite properties in biodiesel. Likewise, the lower cetane number of alcohols could be improved with the simultaneous use of
the higher cetane value of biodiesel. Meanwhile, with the increased
amount of oxygen content in blends, complete fuel combustion can
be achieved. Extensive research has recently been carried out on
the use of various methanolbiodiesel and ethanolbiodiesel
blends in diesel engines [5,7,9,21]. From those previous studies,
it has become clear that methanol and/or ethanol blended with
biodiesel decreases NOx and DPM emissions while there are mixed
results in terms of CO and HC emissions depending on the relative
proportion of methanol or ethanol used as well as the engine operating conditions. Recently, Laza et al. [8] and Kumar et al. [18]
revealed that fuel properties such as lubricity, viscosity and cetane
number can also be improved by blending higher alcohols with
biodiesel. These blended fuels were more suitable for applications
in diesel engines than methanolbiodiesel or ethanolbiodiesel
blends. Subsequently, Tosun et al. [19] compared the effects of
blending 20% methanol, ethanol and butanol by volume with peanut methyl ester on fuel properties, engine performance, and
exhaust emissions. They concluded that butanolbiodiesel blends
showed higher engine power and torque, higher reductions of CO
emissions than both methanolbiodiesel blends and ethanolbiodiesel blends. Meanwhile, Yilmaz et al. [10], Kumar et al. [18]
and Rakopoulos [20] explored the effects of butanolbiodiesel
blends on diesel engine performance and exhaust emissions,
respectively. These studies revealed the beneficial effects of using
various blends of butanol with diesel fuel on CO, smoke and DPM
emissions at various engine loads.
There has been no systematic investigation on the quality of
engine emissions when being fueled with pentanolbiodiesel
blends, to the best of our knowledge. Meanwhile, the effect of
blending biodiesel with both butanol and pentanol on the physical

and chemical characteristics of diesel particulate emissions

remains unknown. This knowledge is needed in order to improve
our understanding of the environmental and health benefits associated with the use of biodiesel and higher alcohols blends. The
aim of this study was to make a comparative evaluation of the
impact of butanolbiodiesel and pentanolbiodiesel blends on
the performance of diesel engines and on the physico-chemical
characteristics of particulates emitted under different operating
conditions. Specifically, the influence of pure biodiesel, and biodiesel blended with 10% and 20% of butanol or pentanol (by volume)
on particulate mass, volatile and solid particle number concentrations and their size distributions were investigated. This work further examined the effects of these fuel blends on the composition
of carbonaceous particulates including EC (elemental carbon), OC
(organic carbon), WSOC (water-soluble organic carbon), and the
toxic polycyclic aromatic hydrocarbons (PAHs). We selected a
non-road diesel engine for this study as such engines are widely
used and emit a substantial fraction of DPM on a global level
because they have limited emission control measures. For example, the U.S. Environmental Protection Agency (EPA) estimates that
non-road diesel engines contribute to about 44% of the DPM emissions nationwide [22]. Similar diesel engines have been used in
other studies for investigating the influence of higher alcohols/biodiesel blends on engine exhaust emissions [18,20]. However, these
engines are different from those used in on-road vehicles,
equipped with modern technology. The outcome of the current
study may offer insights into the effect of biodiesel blended with
higher alcohols on the quality of particulate emissions from nonroad diesel engines, and prove to be useful for future assessments
of environmental and health benefits of these fuel blends.
2. Experimental setup
2.1. Test engine and fuels
The schematic of the experimental system employed in this
study is shown in our previous publication [23]. Experiments were
carried out on a single cylinder, naturally aspirated, four-stroke,
direct-injection diesel engine (L70AE, Yanmar Corporation) connected to a 4.5 kW generator. The diesel engine has a displacement
of 296 cm3 with bore and stroke of 78 and 62 mm, a fixed speed of
3000 rpm (revolutions per min). The main specifications of the
engine are shown in [23]. The fuels used include ultralow sulfur
diesel (ULSD) with less than 10 ppm (parts per million) by weight
of sulfur, methyl esters of waste cooking oil (WCO) as biodiesel, nbutanol (SigmaAldrich, 99.8%, anhydrous), and n-pentanol
(SigmaAldrich, 99%, anhydrous). The biodiesel used in this study
was obtained from Alpha Biodiesel Pte Ltd in Singapore, and the
fuel properties are provided by the biodiesel supplier. The two
kinds of blended fuels were prepared by the volume proportion
of 10% and 20% of each alcohol in biodiesel, and are identified as
B90Bu10, B80Bu20 for the butanolbiodiesel blends and B90P10,
B80P20 for the pentanolbiodiesel blends, respectively. Pure diesel
fuel and biodiesel are identified as D100 and B100, respectively.
The major properties of each fuel are provided in Table 1.
2.2. Particulate sampling and testing
A two-stage Dekati mini-diluter (DI-2000, Dekati Ltd) was used
for diluting the exhaust gas for particulate sampling and online
testing. The diluter provides primary dilution in the range of
8:16:1, depending on the engine operating conditions, while the
secondary dilution system provides a further dilution of 8:1. The
actual dilution ratio for each stage was determined by simultaneously measuring CO2 concentrations in the raw exhaust, in the

73

Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

Table 1
Propertiesa of fuels used in this study.

Properties

ULSD

Biodiesel

n-Butanol

n-Pentanol

Chemical formula
C (wt.%)
H (wt.%)
O (wt.%)
Sulfur content (mg/kg)
Lower heating value (MJ/kg)
Heat of evaporation (kJ/kg)
Density (kg/m3)@15 C
Viscosity (mPa s)@40 C
Cetane number
Flash point (C)
Boiling point (C)
Ignition temperature (C)

86.6
13.4

<10
42.5
250290
827
2.86
52
71
210235
200220

78
12
10
3.1
39.1
300
884
4.36
58
170
338

C4H9OH
64.9
13.5
21.6

33.1
585
810
2.22
17
35
117
343

C5H11OH
68.2
13.6
18.2

34.7
308
814
2.88
20
49
138
300

Data have been taken from Refs. [1113].

background air and in the diluted exhaust [11], using a nondispersive infrared analyzer (MRU VarioPlus, Germany, 0.5% accuracy). This measurement was done for every test, and all data presented in this article have been dilution-corrected to represent
engine-out conditions.
The first stage diluter was only used to cool the sampling gas
temperature below 52 C for particulate sampling. DPM emissions
from the first-stage diluter were collected onto 47 mm Teflon filters (Pall Life Sciences) and pre-combusted (650 C for 12 h)
47 mm quartz fiber filters (Whatman, USA), by using two MiniVol particulate samplers (Air metrics Ltd.; 5 L/min flow rate),
respectively. Particles collected on the Teflon filters were used
for gravimetric analysis, and for WSOC analysis, while those
collected on quartz fiber filters were processed for subsequent
OC/EC and PAHs analysis. Before and after sampling, the filters
were allowed to equilibrate in a humidity-controlled chamber at
a constant temperature and humidity (24 1 C, 30 8% RH), and
weighed using a microbalance (Sartorius MC5, accuracy of 1 lg)
for quantifying total particulate mass emissions. After being
weighed, the filters were kept in glass petri dishes and stored
under refrigeration at 20 C for the subsequent analysis.
The number concentrations and size distributions of volatile
and solid particles in the secondary dilution stage were measured
by a Fast Mobility Particle Sizer (FMPS, Model 3091, TSI Incorporated, USA) in the size range of 5.6560 nm. In this setup, two
diluters were used in series, with the first stage being heated by
a surface heater to 190 C in order to minimize thermophoretic
deposition. For the online measurement of the solid particle number concentrations, a thermodenuder (TD, Dekati Ltd) was placed
in-line between the secondary stage diluter and the FMPS. In the
TD, the volatile compounds of the particles were vaporized by
heating the sample aerosol, and were then gradually cooled and
adsorbed onto active charcoal so that they did not re-condense
onto the remaining solid particles. The temperature in the heating
section of the TD was maintained at 265 C. The TD diffusion losses
were estimated using the method of Surawski et al. [24] and the
diffusion loss-corrected particle size distributions are presented
in this article.
2.3. Carbon analysis
A DRI Model 2001A Thermal/Optical Carbon Analyzer (Atmoslytic Inc., Calabasas, CA, USA), following the IMPROVE TOR (thermal
optical reflection) protocol was used to quantify OC and EC fraction
of particles. In this method, eight carbon fractions can be defined
including OC1-OC4, OP and EC1-EC3. The method details, including
heating program and the determination of each carbon fractions
were described in [25]. For the measurement of water-soluble

organic carbon (WSOC), the particles collected on Teflon filters

were firstly extracted with organic-free Milli-Q water
(>18 MX cm) using a water-bath sonicator (Elmasonic S60H,
ELMA, Germany) for 30 min, and then were filtered through
0.20 lm PTFE membrane filter(Sartorius, Germany). Finally,
0.1 ml of 2 M HCl was added to 5 ml water extracts, was purged
10 min with ultrapure air (80 ml/min), and then 100 ll of solution
was injected into an organic carbon analyzer (TOC-VCSH, Shimadzu) for determination of WSOC.
2.4. Particle-phase PAHs
Particle-phase PAHs were extracted from the quartz filter samples in 50/50 hexane/acetone (HPLC-grade, Fisher Scientific) mixture using a closed vessel microwave-assisted extraction system
(MLS-1200 mega, Mileston, Italy) in accordance with the US EPA
method 3546 [26]. The method details, including sample preparation, calibration standards and the chemical analysis of 16 US priority PAHs by gas chromatography/mass spectrometry (Shimadzu
GCMS-QP 2010, Japan), as well as the performance characterization have been discussed in our previous publication [27]. In this
study, the 16 US priority PAHs were measured and separated into
three different molecular weight ranges, namely low molecular
weight PAHs (LMW-PAHs), medium molecular weight PAHs
(MMW-PAHs) and high molecular weight PAHs (HMW-PAHs), as
described in [28]. Therefore, the total-PAH data represents the
sum of the 16individual PAHs. The overall toxicity is defined as
the sum of Benzo[a]pyrene equivalent (total BaPeq), which was
estimated based each PAH concentration multiplied by its toxicity
equivalent factor (TEF) as recommended by Nisbet and LaGoy [29].
2.5. Statistical analysis
Experiments were performed at a constant engine speed of
3000 rpm and at three engine loads, corresponding to 25%, 50%
and 75% related power, respectively. At each mode of operation,
the engine was allowed to run at least for half an hour until the
exhaust gas temperature and the power output attained steadystate values and data were measured subsequently. For particulate
mass determination, three independent measurements were carried out for each operating condition with particulate samples collected in duplicates for each measurement. For determining
particle number and size distributions, five measurements were
taken at each mode of operation and the corresponding mean values were calculated. In this study, the gaseous emission concentration and fuel consumption were also determined, based on which
the emission volumetric concentrations were converted into mass
factors by using the fuel flow method [30]. Statistical analysis of

74

Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

the experimental data acquired in this study was performed using

the GraphPad Prism software (GraphPad, San Diego, CA), and
statistical significance was ascertained by two-way analysis of
variance (ANOVA) followed by Tukeys multiple comparisons tests.
Values of p < 0.05 were considered significant. The results of particle number size distributions are reported as the mean values, with
the relative standard deviations ranging from 2.5% to 3.1%. All
other reported values are represented as mean SD (standard
deviations).
3. Results and discussion
3.1. Engine performance
For each testing mode, the volumetric flow rates of the fuels
were measured and then converted into the mass consumption
based on the density of each fuel. The brake specific fuel consumption (BSFC) and the brake thermal efficiency (BTE) were then calculated and the results are shown in Fig. 1. The BSFC decreases while
the BTE increases with an increase in the engine load for all tested
fuels due to the higher engine load associated with the more efficient combustion. The BSFC for biodiesel is expected to increase
around 11.814.6% in relation to diesel fuel since the loss of LHV
of biodiesel. Furthermore, both butanol and pentanol have a lower
LHV than that of biodiesel, which lead to an increase in the BSFC for
B90Bu10, B80Bu20 and B80P20 by 1.8%, 3.9% and 2.0%, respectively
at low engine load. The BSFC for B80Bu20 increases by 1.9% at
medium engine load compared to pure biodiesel. In other cases,
the blended fuels show no significant changes in BSFC compared
to biodiesel, indicating the improved combustion characteristics
under these conditions.
In this study, there is a marginal variation in BTE when the
engine combusted biodiesel. When compared to B100, the BTE
for B90P10 increases by 1.5%, 2.0% and 2.1%, from low to high
engine load, and for B80P20 increases by 1.8% and 2.0% at medium
and high engine loads, respectively. As for butanolbiodiesel
blends, only B80Bu20 at high engine load show a 1.6% increase
in BTE. The variation of the BTE with butanol or pentanol addition
can be explained by the different fuel properties combined with
their unique combustion characteristics. On the one hand, the

25% Load

BSFC (g/kW.h)

520

a,b,c
a,b,c
a,c a,b,c
a

50% Load
BSFC

40
75% Load
a,b
a,b
c a,b,c

a,b,c a,b
c
a,c
a
a,c a,b a

390

35

BTE
30
a a,c a,c a a

25

260

130

a,b,c a,c
a a,c
a,c

BTE (%)

650

20

15

0
B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

Test Fuel
Fig. 1. Brake specific fuel consumption (BSFC) and brake thermal efficiency (BTE).
a
Significantly different from the diesel fuel (p < 0.05); bSignificantly different from
the biodiesel (p < 0.05); cSignificantly different between butanolbiodiesel blends
and pentanolbiodiesel blends with the same proportion of them in blends
(p < 0.05).

addition of butanol and pentanol to biodiesel can result in the oxygen enrichment, the higher flame speed, the improved spray characteristics [1,7], and the longer ignition delay associated with their
lower cetane number [20], which could enhance the combustion
process and therefore increase BTE. On the other hand, the higher
latent heat of evaporation of butanol could lower the combustion
temperature and reduce the BTE, especially at lower engine load
with high proportion of them in blends. Compared to butanol,
pentanol has lower latent heat of evaporation, and is therefore less
affected by the variation of combustion temperature. The integrated result shows that the butanol addition only slightly
increased the BTE at high engine loads with 20% butanol addition,
while the pentanol addition shows a slight increase in the BTE for
all tested conditions. Overall, the results on the engine performance indicate that pentanoldiesel blends show less variations
in BSFC and a slightly higher BTE, and are therefore more suitable
for applications in diesel engines compared to butanoldiesel
blends.
3.2. DPM and carbonaceous matter emissions
In this study, the particulate mass emissions, and carbonaceous
matter in particles, including EC, OC, and WSOC were determined,
based on which the ratios of OC/EC and WSOC/OC were calculated.
As shown in Fig. 2, for each fuel, the EC emission factor sharply
increases while the OC and WSOC emission factors generally
decreases with an increase in engine load, resulting in the
decreased OC/EC ratios with engine load. Compared to diesel fuel,
the EC emission factors for biodiesel decrease by 51.3%, 50.3% and
43.1% from low to high engine load. Both the butanol and pentanol
addition to biodiesel result in a further decrease in the EC emissions for all tested conditions. Similar results in smoke or particulate mass reduction were reported for methanolbiodiesel and
ethanolbiodiesel blends [3,5], and for butanolbiodiesel blends
[18,19]. Moreover, with the same proportion of butanol or pentanol in blends, the EC emission reduction for butanolbiodiesel
blends is generally higher than that obtained from pentanolbiodiesel blends, especially at higher engine load with a higher proportion of them in the blended fuels, as shown in Fig. 2(a). For
example, compared to B100, the reduction of EC emission factors
at different proportions of butanol in the blends is 28.555.4%,
28.654.2% and 11.438.7%, respectively from low to high engine
load. However, for pentanolbiodiesel blends, the corresponding
decreases are 23.739.2%, 21.623.5% and 7.19.8%, respectively.
These findings reveal that butanol has higher potential to inhibit
soot emissions than pentanol.
The variation of OC emissions was different from that of EC,
which seems to be associated with the engine load, the type of
alcohols used and the proportion of them in blended fuels. At
low engine load, the OC emissions for biodiesel and for its blends
with alcohols show no significant differences from those for the
diesel fuel. At medium and high engine loads, the OC emission factor for biodiesel is slightly lower than that for diesel fuel. Meanwhile, when compared to B100, the OC emission factors for
B80Bu20 and B80P20 are further reduced by 8.0% and 6.9% at medium engine load, and by 4.7% and 11.4% at high engine load, respectively. The results reveal that the blending of higher proportion of
butanol or pentanol with diesel is effective at reducing OC emissions at higher engine load. It is further observed that at high
engine load, the OC emission factor for B90Bu10 is slightly lower
than that of B90P10, while the OC emission factor for B80Bu20 is
slightly higher than that of B80P20. In other cases, the same proportion of butanol and pentanol in blended fuels results in a similar
emission level of OC.
The results from this study indicate that biodiesel and higher
alcoholsbiodiesel blends are more effective in inhibiting EC

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Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

400

75% Load

50% Load

25% Load

EC
320

240
a

160

a,b,c
a,b,c
a,b,c
a,b,c

80
a

a,b,c
a,b,c
a,b,c
a,b,c

a,b,c
a,b,c
a,b,c
a,b,c

(b)
OC Emission Factor (mg/kW.h)

EC Emission Factor (mg/kW.h)

(a)

900
25% Load

OC
b

720

540
a a a

360

a a,c

50% Load

WSOC

a
a

a
a

150

100

aa a a
a

a a

a,b,c
a,c

50

DPM Mass Emission Factor (mg/kW.h)

WSOC Emission Factor (mg/kW.h)

75% Load

a,b

200

1200
25% Load
1000

800

50% Load

DPM mass

600

a,b,c
a,b,c
a,b,c
a,b,c

200
0
B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

75% Load

(f)

0.40
25% Load

75% Load

50% Load

OC/EC

WSOC/OC

0.32

a,b

a,b

WSOC/OC

a a

OC/EC

a,b a,b a,b,c

a,b,c

400

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

50% Load

a,b,c

27

Test Fuel

45

36

75% Load

a,b,c
a,b,c
a,b
a,b

Test Fuel

25% Load

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

(d)
25% Load

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

Test Fuel

250

a,b,c
a,b,c
a,b,c

18

a,c
a,b,c
a,b,c

180

Test Fuel

(e)

a,b a,b

(c)

75% Load

50% Load

a,b

0.24

a a

a,b,c
a,b,c

a,b
a

a,b,c
a,b,c

0.16

a,b,c

9
a

a,b a,b

a,b,c

0.08
a,b,c
a,b
a a,b
a,b,c

0.00
B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

Test Fuel

Test Fuel

Fig. 2. Emission of carbonaceous species (a) EC (elemental carbon), (b) OC (organic carbon), (c) WSOC (water-soluble organic carbon), and (d) DPM (diesel particulate matter)
mass, and the ratios of (e) OC/EC and (f) WSOC/OC. aSignificantly different from the diesel fuel (p < 0.05); bSignificantly different from the biodiesel (p < 0.05); cSignificantly
different between butanolbiodiesel blends and pentanolbiodiesel blends with the same proportion of them in blends (p < 0.05).

76

Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

emissions than OC emissions. The dramatically reduced EC

emissions coupled with the minor variations of OC emissions for
biodiesel contribute to the increased OC/EC ratios for all tested
conditions, as shown in Fig. 2(e). Addition of higher alcohols to
biodiesel further increases the OC/EC ratios due to further
reduction in the EC emissions, with B80Bu20 having the highest
OC/EC. The results indicate that a high proportion of adsorbed
semi-volatile organics in the particulate matter is emitted from
these blended fuels, especially from B80Bu20. With regard to
WSOC, as shown in Fig. 2(c), it increases significantly for all
blended fuels at all tested conditions when compared to biodiesel,
especially at high engine load. The higher WSOC emissions also
lead to higher WSOC/OC ratios for these blended fuels. The results
indicate that the blended fuels tend to increase the water solubility
of OC, suggesting increased emissions of polar organic compounds
because of the increased oxygen contents in the blended fuels.
EC results from fuel droplet pyrolysis in the fuel-rich zone
under high pressure and temperature [31]. Therefore, the increase
in EC emissions with engine load is consistent with the higher fuel
usage, lower air/fuel ratio, and higher pressure and temperature at
higher loads [31]. Both biodiesel and higher alcohols used in this
study are oxygenated with no aromatic compounds. The oxygen
in the fuel could be effectively delivered to the pyrolysis zone of
the burning diesel spray to suppress soot formation, leading to
reduction in EC emissions. Meanwhile, the absence of aromatics
in biodiesel and its blends with higher alcohols could reduce the
soot precursors in the engine combustion process and therefore
lead to lower EC formation and emissions. The lower EC emissions
contribute to the lower DPM emissions. Compared to B100, the
blended fuels contain more oxygen, which could further reduce
EC and DPM emissions. Meanwhile, as observed in our previous
study, oxygenated fuels with a low cetane number could reduce
the amount of soot formed and its emissions because the lower
cetane number leads to an increase in ignition delay and the
amount of fuel burned in the premixed combustion phase [32].
The improved combustion of oxygenated fuels might be responsible for the lower EC emissions from both butanol and pentanol
addition. In addition, as explained by Sukjit et al. [1] and Yoshimoto and Onodera [33], the improved fuel atomization and evaporation in the cylinder, associated with the addition of alcohols,
might also contribute to lower EC and DPM emissions. In this
study, it appears that the higher oxygen content and the lower
cetane number for butanolbiodiesel blends are more effective in
reducing soot formation than that for pentanolbiodiesel blends,
and therefore lead to lower EC emissions.
There are several factors that can be considered to explain the
variation of OC emissions. On the one hand, the oxygen content
in biodiesel and in blended fuels might lead to lower OC emissions
due to the enhanced combustion. Furthermore, the lower EC emissions for these fuels provided a small surface area for adsorption of
the volatile substances that comprised the OC, resulting in lower
OC emissions. On the other hand, the OC emissions could also be
influenced by the physical properties of each fuel. For example,
the higher boiling point, higher viscosity and higher density of biodiesel could lead to a poor air/fuel mixture and incomplete combustion, and thus higher OC emissions [1]. The lower cetane
number of both butanol and pentanol, and the higher heat of
vaporization of butanol could cause a decreased ignitability and
flammability, leading to higher unburned hydrocarbon (HC) emissions as reported in previous studies [10,20] and thus the higher
OC emissions. In this study, there is a marginal variation of OC
emissions when the engine was fueled with biodiesel and the
blended fuels, suggesting that the fuel properties were one of the
main factors that caused the variation of OC emissions. The disadvantage of these fuel properties could be attenuated with a higher
engine load as the higher engine load is associated with higher fuel

injection pressure and higher combustion temperature, leading to

slightly lower OC emissions from both biodiesel and blended fuels
when compared to diesel fuel.
3.3. Particle-phase PAHs emissions
As shown in Table 2, when compared to diesel fuel, the total
PAHs emission factor for B100 is reduced by 14.823.1% from different engine loads. These variations are mainly contributed by the
reduction of LMW-PAHs and HMW-PAHs, while the MMW-PAHs
show a slightly lower or higher emission factor than that of diesel
fuel. The lower PAHs emissions also lead to the lower total BaPeq.
In addition, the reduction of total BaPeq is higher than that of total
PAHs due to the significant reduction in the emission of HMWPAHs, which have relatively higher toxicity. The significant reduction in the emission of particle-phase PAHs as well as total BaPeq
for waste cooking oil-based biodiesel has been reported in the literature [28,34]. Meanwhile, Lu et al. [28] found that biodiesel was
more effective in the reduction of both LMW-PAHs and HMWPAHs than that of MMW-PAHs. The finding in this study is consistent with those previously reported [28,34]. When blending of
butanol or pentanol with biodiesel, the total particle-phase PAHs
emissions are further reduced, with the higher proportion of butanol or pentanol in the blends resulting in the lower PAHs emissions. The variations are mainly contributed by the reduction of
MMW-PAHs and HMW-PAHs, while the LMW-PAHs showe a
slightly lower emission factor for butanolbiodiesel blends and
higher emission factors for pentanolbiodiesel blends when compared to biodiesel. It is further observed that butanolbiodiesel
blends show lower PAHs emissions than pentanolbiodiesel
blends. Compared to B100, the reduction of total particle-phase
PAHs emission factors at different proportions of butanol in the
blends are 35.759.0%, 44.763.9% and 29.242.3%, respectively
from low to high engine load. As for pentanolbiodiesel blends,
the corresponding decreases are 10.631.7%, 10.436.2% and
17.130.1%, respectively. Compared to biodiesel, a significant
reduction in total BaPeq from the blended fuels is also observed
in this study. Moreover, the same proportion of alcohols in the
blended fuels shows a similar BaPeq although butanolbiodiesel
blends seem to have lower total PAHs emissions than those of pentanolbiodiesel blends. These findings suggest that the blended
fuels decreased the total particle-phase PAHs emissions significantly as well as their corresponding total BaPeq moderately. The
reduction of PAH emissions is mainly attributed to the oxygen
content and the absence of aromatic contents in the biodiesel.
Compared to biodiesel, the blended fuels have higher oxygen contents, which could further improve the combustion and lead to
lower PAH emissions. In addition, with the same proportion of
higher alcohols in the blended fuels, butanolbiodiesel blends have
higher oxygen contents than that of pentanolbiodiesel blends and
therefore led to lower total PAHs emissions.
3.4. Volatile and solid particle number emissions and size distributions
In this study, the volatile particle number (PN) size distributions
varied with the engine load and the fuel type as shown in Fig. 3(a)
(c). In order to analyze the variation of the number concentrations
of ultrafine particles (UFP; aerodynamic diameter (AD) 6 100 nm)
and nanoparticles (NP; AD 6 50 nm) in detail, the volatile particles
were further classified into four size fractions: <15, 1550, 50100,
and >100 nm. The effect of biodiesel and its blended fuels on volatile particle number emission factors in each size fractions shown
in Fig.4. The volatile particle geometric mean diameter (GMD) is
provided in Table 3.
As can be seen from Fig. 3, the variation of volatile particle
number size distributions, caused by biodiesel and its blends with

77

Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

Table 2
Particle-phase PAHs emission factor (lg/kW h) and total BaPeq.
LMW-PAHs

a
b
c

MMW-AHs

HMW-PAHs

Total-PAHs

Total-BaPeq

55.3 13.4
13.1 5.6a
6.8 2.2a,b
5.9 1.5a,b
4.8 0.3a,b
4.4 1.0a,b

414.5 66.9
341.3 31.4
291.4 20.7a,b
305.1 38.4a
140.2 20.3a,b,c
233.1 25.0a,b,c

21.3 4.6
5.0 1.8a
2.6 0.8a,b
2.4 0.5a,b
1.5 0.2a,b
1.6 0.3a,b

25% load
D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

103.8 24.8
25.9 11.2a
18.1 4.0a,c
42.1 6.5a,b,c
20.4 9.3a,c
34.4 10.2a,c

255.5 28.7
302.2 14.6a
194.6 14.5a,b,c
257.0 30.4b,c
114.8 10.7a,b,c
194.3 13.8a,b,c

50% load
D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

68.4 13.4
22.0 5.1a
12.5 1.6a,b,c
34.5 5.9a,b,c
15.0 4.9a,c
23.9 5.0a,c

255.1 14.2
260.0 17.7
145.1 17.4a,b,c
223.4 11.4a,b,c
87.6 7.4a,b,c
158.8 17.1a,b,c

17.3 3.9
8.6 1.9a
3.1 0.5a,b
2.7 0.4a,b
2.5 0.2a,b
2.7 0.5a,b

340.9 31.5
290.6 24.7
160.8 19.5a,b,c
260.5 17.6a,b,c
105.0 12.4a,b,c
185.4 22.5a,b,c

10.0 2.2
3.4 0.6a
1.4 0.2a,b
1.4 0.2a,b
1.1 0.1a,b
1.3 0.2a,b

75% load
D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

80.3 7.4
21.2 4.1a
16.6 1.5a,c
33.6 2.5a,b,c
24.5 1.7a,c
31.0 4.2a,b,c

384.0 11.3
338.2 7.6a
237.6 8.0a,b,c
266.6 14.5a,b,c
181.9 13.6a,b,c
221.6 13.4a,b,c

12.1 1.6
6.9 1.2a
5.1 0.9a,b,c
3.9 0.4a,b,c
5.1 0.8a,b,c
3.4 0.2a,b,c

476.4 20.3
366.3 12.9a
259.3 10.4a,b,c
303.8 17.5a,b,c
211.4 16.1a,b,c
256.0 17.8a,b,c

6.6 0.7
3.1 0.4a
2.2 0.3a,b
2.2 0.2a,b
1.8 0.3a,b
1.5 0.1a,b

Significantly different from the diesel fuel (p < 0.05).

Significantly different from the biodiesel (p < 0.05).
Significantly different between butanolbiodiesel blends and pentanolbiodiesel blends with the same proportion of them in blends (p < 0.05).

higher alcohols, seems to be associated with the engine load. At

low engine load, the size distributions of volatile particle counts
for all tested fuels are bimodal, showing clearly a distinctive nucleation mode with the peak diameters of 810 nm, and an accumulation mode with the peak diameters of 4552 nm, respectively.
The peak of accumulation mode particles for biodiesel is similar
to that for diesel, with the peak shifting toward to smaller size.
However, the peak of nucleation mode particles for biodiesel significantly increases at low engine load. The variations of particle
size distributions for biodiesel are mainly caused by the increase
in particles of less than 50 nm, while the particles of larger than
50 nm show lower counts than those of diesel fuel, as evident from
Fig.4. The variations also cause a decrease in GMD, as shown in
Table 3. When blending butanol or pentanol with biodiesel, the
size distribution profiles of their nucleation mode particles shift
further upward while those of accumulation mode particles in general became flatter, indicating a further increase in the counts of
nucleation particles, a further decrease in these larger particles,
and a further decrease in GMD, as shown in Fig. 4 and Table 3,
respectively. Moreover, with the same proportion of higher alcohols in the blended fuels, the butanolbiodiesel blends show a larger increase in these nucleation mode particles and a smaller
decrease in the accumulation mode particles than those of pentanolbiodiesel blends. Specifically, when compared to biodiesel,
the emission factors of particles of less than 15 nm increase by
23.6%, 6.5%, 10.9% and 5.9% for B90Bu10, B90P10, B80Bu20 and
B80P20, respectively. However, for particles of larger than 15 nm,
the corresponding decrease is 7.1%, 18.9%, 17.9% and 24.6%, respectively. The combination of the reduced larger particles with the
increased smaller particles result in the total counts of particles
for B90P10 decreased by 11.4%, while for B80Bu20, it increases to
19.6%, when compared to that for biodiesel. As for B90Bu10 and
B80P20, the total particle counts show no significant different from
that of biodiesel.
At medium and high engine loads, the particle size distribution
shifts from the bimodal mode to the single mode, and upward
more toward the larger size. At these loads, the peak of particles
size distributions for biodiesel is lower than that of diesel fuel, with
the peak shifting toward smaller size, resulting in a decrease of

total particle number emissions and GMD, as evident from Fig. 4

and Table 3, respectively. The particle size distribution profiles in
general becomes flatter with the addition of both butanol and pentanol to biodiesel, which is in line with the results from Fig. 4 that
the particle number emission factors for blended fuels were less
than those of biodiesel. In addition, B90Bu10 shows lower total
particle counts than B90P10. When compared to B90Bu10,
B80Bu20 increases the total particle counts again, which results
in the B80Bu20 having higher total particle counts than that of
B80P20. It is further observed from Fig. 4 that compared to diesel,
the lower emissions of the total particle counts for both biodiesel
and the blended fuels is mainly caused by the reduction of the particles of larger than 50 nm, but the particles of less than 50 nm
were increased. Moreover, compared to B100, except that a slight
increase in particles of less than 50 nm is found forB80Bu20 at
medium and high engine loads, and for B80P20 at high engine load,
other blended fuels show no significant changes in particles of less
than 50 nm, but only decreased the lager particles. The results indicate that the reduction of total particle number emissions as well
as the GMD associated with both butanol and pentanol addition
is a result of a significant reduction in the number of larger particles. The reduction in larger particles is responsible for the
decrease in particulate mass, as shown in Fig. 2, as they are more
influential on mass than smaller particles.
The formation of DPM occurs in two stages. First, soot or solid
particles are produced in the engine combustion chamber by processes that include nucleation, surface growth, and agglomeration
[35]. Second, during the dilution and cooling process in the exhaust
pipe, the soluble organic fraction (SOF) nucleates to form new particles, or adsorbs onto or absorbs into existing particles [35]. Therefore, the factors that affect the engine combustion process
determine the soot particle emissions, while the states of the dilution and cooling processes affect the relative amounts of volatile
substances that adsorb or condense onto existing particles and
nucleate to form new particles. As can be seen in Fig. 5, the solid
particle number and surface area concentrations increase with
the engine load for all the fuels used in this study. It is possible that
the higher viscosity and the higher boiling point of biodiesel, which
lead to the variations of the fuel injection pressure of the

Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

dN/dlog (Dp) (#/cm3)

(a)

5x10

25% Load
4x10

3x10

2x10

1x10

D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

0
10

100

Diameter (nm)
7

6.4x10

4.8x10

3.2x10

1.6x10

dN/dlog (Dp) (#/cm3)

(b) 8.0x10

50% Load

D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

0.0
10

100

Diameter (nm)

dN/dlog (Dp) (#/cm3)

(c)

2.0x10

75% Load
1.6x10

1.2x10

8.0x10

4.0x10

D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

0.0
10

100

Diameter (nm)
Fig. 3. Volatile (without TD) PN (particle number) size distributions.

9.0

7.2
a,b,c

75% Load
Dp>100 nm
Dp=50-100 nm
Dp=15-50 nm
Dp<15 nm

a,b,c
a

5.4

50% Load

25% Load

a,c

b,c
a
a

a,b,c
a,c
a,b,c

a,b,c

3.6

a,b,c
a,b,c a,b,c
a,b,c

1.8

0.0
B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

mechanical fuel injection system and atomization characteristics,

result in the variation of the solid particle counts. After adding
butanol or pentanol to biodiesel, the reduced carbon content coupled with an increase in oxygen content, the increased premixed
combustion and reduced diffusion combustion, and the improved
fuel properties may lead to better combustion and therefore contribute to the reduction of total solid particle counts and surface
area. This finding, therefore, confirms that less soot particles are
generated in the cylinder from these blended fuels and therefore

lead to lower volatile particle number emissions from medium

and high engine loads, as shown in Fig. 4. However, at low engine
load, the combination of high SOF and relatively low solid particle
counts may have caused an extensive nucleation of the SOF to form
a very large nuclei mode and therefore an obvious peak of nucleation mode particles. Compared to diesel fuel, the decreased surface area of solid particles, the increased condensation of volatile
and semi-volatile species from biodiesel, promote the formation
of nanoparticles by homogenous nucleation as evident from
Fig. 3(a). This increase in the nucleation mode particles results in
an increase of the total particle number concentration from biodiesel. The increase in the nucleation mode particles is further
enhanced with the addition of both butanol and pentanol to biodiesel fuel, resulting in a further increase in nucleation particle
counts as shown in Fig. 4. The observations suggest that the formation of some new particles from volatile species after the dilution
and cooling processes is a contributor to the increase in total particle counts, for both biodiesel and the blended fuels.
From the observations of this study, we can conclude that
blending up to 20% butanol or pentanol with biodiesel show minor
variations in the engine performance but can effectively reduce the
particle mass and elemental carbon emissions, lower total particlephase PAHs and their carcinogenic potential, and decrease total
counts of volatile and solid particles. However, both the blended
fuels are significantly increased in the fraction of OC and WSOC
in particles. In addition, the reduction of total particle number concentrations with the addition of both butanol and pentanol is a
result of a significant reduction in the number of particles larger
than 50 nm, while the blended fuels show higher counts of particles of less than 15 nm at low engine load. The results from this
study also reveal that with the same proportion of butanol or pentanol in the blended fuels, the butanolbiodiesel blends have
higher potential to inhibit EC and lower particle-phase PAH emissions than the pentanolbiodiesel blends. The change in the diesel
particle characteristics, caused by the combustion of these longchain alcoholsbiodiesel blends, seems to be associated with the
engine load, the type of alcohols used and the proportion of them
in the blended fuels, and more importantly, could have important
implications for ambient health studies.

Volatile PN Emission Factor (#/kW.h) [1014]

78

Test Fuel
Fig. 4. Size-segregated volatile particle number emissions and GMD (geometric
mean diameter). aSignificantly different from the diesel fuel (p < 0.05); bSignificantly different from the biodiesel (p < 0.05); cSignificantly different between
butanolbiodiesel blends and pentanolbiodiesel blends with the same proportion
of them in blends (p < 0.05).

Z.-H. Zhang, R. Balasubramanian / Applied Energy 163 (2016) 7180

Table 3
Geometric mean diameter (GMD, nm) of particles.
25% load
D100
B100
B90Bu10
B90P10
B80Bu20
B80P20

35.9 1.3
29.9 1.0
21.2 1.6
22.3 1.4
17.7 0.6
19.4 0.8

a
a,b,c
a,b,c
a,b,c
a,b,c

50% load

75% load

56.0 1.8
46.2 1.6a
44.6 1.7a,b
44.6 0.8a,b
43.4 1.5a,b
43.9 0.7a,b

74.4 2.7
59.3 1.8a
57.4 1.5a,b,c
58.3 1.6a,b,c
54.3 1.9a,b
54.6 2.3a,b

Significantly different from the diesel fuel (p < 0.05).

Significantly different from the biodiesel (p < 0.05).
Significantly different between butanolbiodiesel blends and pentanolbiodiesel blends with the same proportion of them in blends (p < 0.05).

79

exhibited a major reduction of particles larger than 50 nm.

However, for the both blended fuels, there is a significant
increase in the emission of particles of with diameter less
than 15 nm at low engine load, which in turn leads to the
increase in the total particle counts for butanolbiodiesel
blends at low engine load.

Acknowledgements

20

50% Load

75% Load

References

6
16

Solid PN
5

Solid PA

4
3

a,b,c
a,b,c a,b,c
a,c

a
1

a,c
a,b
a,b

a,b,c

a,b,c
a a,ba,b a,b,c

a,b,c
a a,c a a,b

a a,b,c
a,b,c a,ba,b

12

a a,ba,ba,ba,b

Solid PA Conc. [m2/cm3] [105]

Solid PN Conc. [#/cm3] [107]

25% Load

Zhi-Hui Zhang would like to thank the SingaporePekingOxf

ord Research Enterprise (COY-15-EWI-RCFSA/N197-1) for providing scholarship in support of his doctoral study.

0
B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

B80P20
B80Bu20
B90P10
B90Bu10
B100
D100

Fuel Type
Fig. 5. Solid PN (particle number) and solid PA (particle area) concentrations.
a
Significantly different from the diesel fuel (p < 0.05); bSignificantly different from
the biodiesel (p < 0.05); cSignificantly different between butanolbiodiesel blends
and pentanolbiodiesel blends with the same proportion of them in blends
(p < 0.05).

4. Conclusions
The following major conclusions were drawn from this preliminary study.
(1) Compared to biodiesel, butanolbiodiesel blends show a
maximum of 1.6% increase in the brake thermal efficiency
(BTE) and a 1.93.9% increase in the brake specific fuel consumption (BSFC) at low and medium engine loads. Pentanolbiodiesel blends result in an improvement in the
BTE and a maximum of 2% increase in the BSFC.
(2) Compared to biodiesel, both the blended fuels can effectively
reduce the elemental carbon (EC) and particulate mass emissions, with butanol being more effective than pentanol. The
blended fuels also reduce OC emissions at higher engine
loads with higher proportion of them blends. However, the
blends increase the OC and WSOC fraction in particles, especially for 20% butanol in the blended fuels at low engine
load.
(3) Compared to biodiesel, the addition of both butanol and
pentanol show lower emissions of total particle-phase PAHs
and also lower carcinogenic potential.
(4) Both of the blended fuels can effectively reduce in the total
volatile number emissions at medium and high engine loads.
The reduction of the total particle counts is mainly caused by
the reduction of solid particle emission in the cylinder, and

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